Color material dispersion liquid, composition, film, optical filter and display device

ABSTRACT

A color material dispersion liquid including a color material, which is a salt-forming compound of an organic dye with a heteropolyoxometalate, a dispersant and a solvent, wherein the organic dye is at least one organic dye selected from the group consisting of a porphyrin dye, a tetraazaporphyrin dye, a phthalocyanine dye and a squarylium dye, and wherein the heteropolyoxometalate is a heteropolyoxometalate which has an oxidation-reduction potential larger than −0.3 V relative to the silver/silver chloride electrode.

TECHNICAL FIELD

The disclosure relates to a color material dispersion liquid, acomposition, a film, an optical filter and a display device.

BACKGROUND ART

In recent years, white LEDs are often used as the light sources oflighting instruments or display devices. The white LED has several typesof light emitting methods, such as a method for obtaining white light byarranging R (red), G (green) and B (blue) light emitting LEDs, and amethod for obtaining white light by combining blue light emitted from ablue LED with yellow light emission from a yellow fluorescent substance.In the case of using, of these methods, the method for obtaining whitelight by combining the blue LED with the yellow fluorescent substance,the spectrum of the thus-obtained white light includes, a light inorange color in a range around 590 nm and a light in cyan color around490 nm, and it is known that as the light emission intensity of thelight in this range increases, the color rendering properties decrease.

To eliminate unnecessary light emitting components and obtain vividdisplay colors, an optical filter is conventionally disposed on thefront surface of a display device.

For example, to suppress a decrease in the color purity of a plasmadisplay caused by neon light, an optical filter containing atetraazaporphyrin compound which has an absorption maximum wavelength ina wavelength range of around 570 nm to 600 nm, for example, is disclosed(Patent Documents 1, 2).

However, there is a problem of deterioration of optical properties,since the organic dye is likely to deteriorate when the optical filtercontaining the organic dye is used for a long period of time. To solvethe problem, various kinds of additives have been proposed, such as amethod of adding a combination of a hindered amine compound and atriazine compound to a porphyrin derivative compound (Patent Document 3)and a method for adding a specific triphenylamine to a tetraazaporphyrincompound (Patent document 4).

As a method for suppressing a deterioration of the organic dye, forexample, for the purpose of providing such an optical filter thatexcellent light resistance and moist heat resistance are exhibited inthe pressure-sensitive adhesive layer, inserting a dye cation in alayered cray mineral such as smectite, has been proposed (PatentLiterature 5). As a color material excellent in heat resistance andlight resistance, the inventors of the present invention have proposed acompound in which salt is formed between an aminium or diimonium dye anda heteropolyoxometalate anion (Patent Document 6).

CITATION LIST Patent Documents

Patent Document 1: Japanese Patent No. 3834479

Patent Document 2: Japanese Patent No. 4485778

Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No.2006-56913

Patent Document 4: JP-A No. 2012-63629

Patent Document 5: Japanese Patent No. 5020258

Patent Document 6: JP-A No. 2015-48432

SUMMARY OF INVENTION Technical Problem

To suppress light in an unnecessary wavelength range, which is caused bya light source, an optical member or outside light reflection, it seemseffective to use a dye that selectively absorbs the light in theunnecessary wavelength range. However, conventional dye compounds stillhave a problem of poor light resistance, and the prior art as describedabove cannot obtain a film that is excellent in light resistance, whilesuppressing a decrease in light transmission efficiency and selectivelyand effectively reducing the light in the unnecessary wavelength range.

The disclosed embodiments were achieved in light of the abovecircumstances. An object of the disclosed embodiments is to provide acolor material dispersion liquid and a composition, both of which canform a film that is excellent in light resistance while selectively andeffectively reducing the light in the unnecessary wavelength range; afilm and an optical filter, both of which are excellent in lightresistance, while selectively and effectively reducing the light in theunnecessary wavelength range; and a display device comprising theoptical filter and decreasing the light in the unnecessary wavelengthrange.

Solution to Problem

In a first embodiment, there is provided a color material dispersionliquid comprising a color material, which is a salt-forming compound ofan organic dye with a heteropolyoxometalate, a dispersant and a solvent,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

In another embodiment, there is provided a composition comprising acolor material, which is a salt-forming compound of an organic dye witha heteropolyoxometalate, and a binder component,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

In another embodiment, there is provided an optical filter comprising acolor material, which is a salt-forming compound of an organic dye witha heteropolyoxometalate,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

In the color material dispersion liquid, composition and optical filterof the disclosed embodiments, the heteropolyoxometalate of thesalt-forming compound may be a heteropolyoxometalate containingvanadium.

In the color material dispersion liquid, composition and optical filterof the disclosed embodiments, the color material may be at least onesalt-forming compound selected from the group consisting of asalt-forming compound represented by the following general formula (1)and a salt-forming compound represented by the following general formula(3):

where R¹ to R¹² each independently represent a hydrogen atom, a halogenatom, a nitro group, a cyano group, a hydroxy group, an amino group, acarboxyl group, a sulfonic acid group, an alkoxy group optionallycontaining a substituent, an aryloxy group optionally containing asubstituent, a monoalkylamino group optionally containing a substituent,a dialkylamino group optionally containing a substituent, an alkylthiogroup optionally containing a substituent, an arylthio group optionallycontaining a substituent, an alkyl group optionally containing asubstituent or an aromatic ring group optionally containing asubstituent; X represents a carbon atom or a nitrogen atom; and when Xis a nitrogen atom, R⁹ to R¹² are not present; or R¹ and R², R³ and R⁴,R⁵ and R⁶, R⁷ and R⁸ may each independently form a ring, and the ringmay contain an unsaturated bond;

A^(c−) represents a heteropolyoxometalate anion which is a c-valentanion and which has an oxidation-reduction potential larger than −0.3 Vrelative to the silver/silver chloride electrode; a, b and c are each aninteger of 2 or more; d is an integer of 1 or more; and the salt-formingcompound is a normal salt that a×b=c× d,

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent organicgroup; Z⁺ represents an organic cation group; e represents an integer offrom 1 to 4; and when e is 2 or more, a plurality of Ys and a pluralityof Z⁺s may be each the same or different;

A^(c−) represents a heteropolyoxometalate anion which is a c-valentanion and which has an oxidation-reduction potential larger than −0.3 Vrelative to the silver/silver chloride electrode; f and c are each aninteger of 2 or more; g is an integer of 1 or more; and the salt-formingcompound is a normal salt that f×e=c×g.

The composition of the disclosed embodiments may further comprise adispersant.

In another embodiment, there is provided a film comprising thecomposition of the disclosed embodiments or a cured product thereof.

In another embodiment, there is provided a display device comprising theoptical filter of the disclosed embodiments.

Advantageous Effects of Invention

According to the disclosed embodiments, the following can be provided: acolor material dispersion liquid and a composition, both of which canform a film that is excellent in light resistance while selectively andeffectively reducing the light in the unnecessary wavelength range; afilm and an optical filter, both of which are excellent in lightresistance, while selectively and effectively reducing the light in theunnecessary wavelength range; and a display device comprising theoptical filter and decreasing the light in the unnecessary wavelengthrange.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings,

FIG. 1 is a schematic configuration diagram of an example of the displaydevice of the disclosed embodiments, and

FIG. 2 is a schematic configuration diagram of another example of thedisplay device of the disclosed embodiments.

DESCRIPTION OF EMBODIMENTS

Hereinafter, descriptions will be made about embodiments, workingexamples and others in the present disclosure with reference to thedrawings and so on. However, about the present disclosure, manydifferent embodiments can be carried out. Thus, the present inventionshould not be interpreted with any limitation to described contents ofthe embodiments, the working examples, and the others, which will begiven as examples. In order to make a description about each of thedrawings clearer, the width, the thickness, the shape and any otherfactors of each part or portion therein may be schematicallyillustrated, differently from that of a part or portion in an actualform. However, the illustrated factors are each a mere example not tolimit the interpretation of the present disclosure. In the documentDESCRIPTION, and each of the drawings, to the same element as in any oneof the drawings referred to already is attached the same referencenumber; thus, a detailed description thereabout may be appropriatelyomitted. For the convenience of the descriptions, any word such as aword “upward” or “downward” may be used. However, the upward anddownward directions may also be reversed.

In the DESCRIPTION, in a case where, for example, any constituent suchas any member or region is “on (or beneath) of a different constituentsuch as a different member or region, examples of this case include notonly a case where the constituent is just on (or just beneath) of thedifferent constituent, but also a case where the constituent is over orabove (or under or below) of the different constituent, that is, a casewhere an additional constituent is included between the two to be overor above (or under or below) the constituent unless otherwise specified.

In the DESCRIPTION, “(meth)acrylic” means any of acrylic andmethacrylic, and “(meth)acrylate” means any of acrylate andmethacrylate.

Also in the DESCRIPTION, the terms “plate”, “sheet” and “film” are basedonly on differences in names and are not distinguished from each other,and the term “film surface (plate surface, sheet surface)” refers to asurface corresponding to, when a target film-shaped (plate-shaped,sheet-shaped) member is viewed wholly from a large perspective, theplanar direction of the target film-shaped member (plate-shaped member,sheet-shaped member).

Also in the DESCRIPTION, the term “organic dye” refers to a compoundwhich is a dye compound containing a carbon atom and which absorbs atleast part of visible light (light of a wavelength of from 400 nm to 700nm) and near-infrared light (light of a wavelength of from 700 nm to1100 nm), and the term “color material” refers to a compound whichabsorbs at least part of visible light (light of a wavelength of from400 nm to 700 nm) and near-infrared light (light of a wavelength of from700 nm to 1100 nm), and it encompasses a compound which absorbsnear-infrared light only.

Also, the term “organic group” refers to a group containing a carbonatom. The term “organic cation” refers to a cation that the cationmoiety contains a carbon atom.

Hereinafter, the color material dispersion liquid, composition, film,optical filter, display device of the disclosed embodiments will bedescribed in sequence.

A. Color Material Dispersion Liquid

The color material dispersion liquid of the disclosed embodiments is acolor material dispersion liquid comprising a color material, which is asalt-forming compound of an organic dye with a heteropolyoxometalate, adispersant and a solvent,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

The color material dispersion liquid of the disclosed embodimentscontains the color material, which is the salt-forming compound of thepredetermined organic dye with the heteropolyoxometalate having anoxidation-reduction potential of larger than −0.3 V relative to thesilver/silver chloride electrode.

The organic dye dissolves in a solvent to form a film. However, sincethe organic dye is likely to aggregate in the film and to deposit, theorganic dye falls into a situation where it is difficult for the organicdye to form a uniform film and, as a result, to effectively anduniformly exhibit the function of selectively absorbing the light of anunnecessary emission wavelength. Also, the organic dye has a longoutstanding problem of poor light resistance.

When the organic dye forms the salt-forming compound with theheteropolyoxometalate, two or more cationized predetermined organic dyesform an ionic bond with one polyvalent heteropolyoxometalate anion.Accordingly, in the color material of the disclosed embodiments, theplural organic dyes are arranged around the heteropolyoxometalate anionto form one molecule, and ion pair formation is possible between themolecules. Accordingly, molecular association is promoted and, as aresult, the color material becomes fine particles hardly soluble in thesolvent.

According to the color material dispersion liquid of the disclosedembodiments, the color material being the salt-forming compound iscombined with the dispersant to disperse the color material in thesolvent by the dispersant. Accordingly, even in the solvent and thefilm, the color material is uniformly dispersed in the state of fineparticles. Accordingly, by using the color material dispersion liquid ofthe disclosed embodiments, the film that can uniformly exhibit thefunction of selectively absorbing the light of the unnecessary emissionwavelength, can be formed. Especially, since the color material of thedisclosed embodiments uses the above-mentioned predetermined organicdye, sharp absorption with a narrow half-width can be realized in atleast all of the visible light range, and various specific wavelengthscan be selectively absorbed depending on the intended application. Theporphyrin dye exhibits absorption with a narrow half-width in a visiblelight wavelength range of from 400 nm to 500 nm, and thetetraazaporphyrin or phthalocyanine dye having a similar skeleton to theporphyrin dye exhibits absorption with a narrow half-width in awavelength range of from 500 nm to 1000 nm. The squarylium dye exhibitsabsorption with a narrow half-width in a wavelength range of from 400 nmto 900 nm.

A point in common between the porphyrin, tetraazaporphyrin andphthalocyanine dyes is that they are organic compounds having a cyclicstructure formed by a combination of four pyrroles. Since they can beturned into a cation by the protonation, etc., of the nitrogen atoms ofthe pyrroles, ion pair formation with the heteropolyoxometalate anion ispossible. Also, since the squarylium dye can be turned into a cation bythe protonation, etc., of the nitrogen atom in the molecule, ion pairformation with the heteropolyoxometalate anion is possible.

Each of the predetermined organic dyes has a fundamental absorptionrange. The absorption maximum can be shifted by the introduction of asubstituent or the extension of a n-electron framework, and ion pairformation with the heteropolyoxometalate anion is possible. Accordingly,depending on the combination thereof, it is excellent in the function ofselectively absorbing the light of the specific wavelength of visiblelight (wavelength 400 nm to 700 nm) and of near-infrared light(wavelength 700 nm to 1100 nm).

When the color material is present in the state of fine particles in thefilm, it is estimated that light deterioration is likely to occur onlyon the particle surface, and the promotion of light deterioration issuppressed.

Also, the inventors of the disclosed embodiments found a new method forsuppressing light deterioration and increasing light resistance.

The discoloration mechanism caused by the light of the organic dye isthought to be a “self-sensitized light singlet oxygen oxidationreaction” described below. The “self-sensitized light singlet oxygenoxidation reaction” is such a mechanism that, first, singlet oxygen isgenerated by the energy which is generated when the organic dye isphotoexcited and returns to the ground state, and the singlet oxygen,which has high reactivity, oxidizes the organic dye, thereby discoloringthe organic dye.

In the disclosed embodiments, a new method for suppressing the singletoxygen generation is used. That is, due to the formation of thesalt-forming compound of the predetermined organic dye with theheteropolyoxometalate having an oxidation-reduction potential largerthan the predetermined value and a property of being easily reduced, theheteropolyoxometalate having a property of being easily reduced absorbsthe energy which is generated when the organic dye is photoexcited andreturns to the ground state, whereby the singlet oxygen generation canbe suppressed during light irradiation. As a result, the lightresistance of the color material being the salt-forming compound isfurther increased.

The color material dispersion liquid of the disclosed embodimentscontains at least a color material, a dispersant and a solvent. Asneeded, it may contain other components.

Hereinafter, the components of the color material dispersion liquid ofthe disclosed embodiments will be described in detail.

(Color Material)

The color material used in the disclosed embodiments is a color materialwhich is a salt-forming compound of an organic dye with aheteropolyoxometalate, and the organic dye is at least one organic dyeselected from the group consisting of a porphyrin dye, atetraazaporphyrin dye, a phthalocyanine dye and a squarylium dye, andthe heteropolyoxometalate is a heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

The at least one organic dye selected from the group consisting of aporphyrin dye, a tetraazaporphyrin dye and a phthalocyanine dye, ispreferably a compound that does not contain a metal atom in the center,since it is cationized by protonation of a nitrogen atom constituting apyrrole ring and is likely to form a salt with the heteropolyoxometalateanion. For example, it may be a compound represented by the followinggeneral formula (1-1):

where R¹ to R¹² each independently represent a hydrogen atom, a halogenatom, a nitro group, a cyano group, a hydroxy group, an amino group, acarboxyl group, a sulfonic acid group, an alkoxy group optionallycontaining a substituent, an aryloxy group optionally containing asubstituent, a monoalkylamino group optionally containing a substituent,a dialkylamino group optionally containing a substituent, an alkylthiogroup optionally containing a substituent, an arylthio group optionallycontaining a substituent, an alkyl group optionally containing asubstituent or an aromatic ring group optionally containing asubstituent; X represents a carbon atom or a nitrogen atom; and when Xis a nitrogen atom, R⁹ to R¹² are not present; or R¹ and R², R³ and R⁴,R⁵ and R⁶, R⁷ and R⁸ may each independently form a ring, and the ringmay contain an unsaturated bond.

In the general formula, as the halogen atom as R¹ to R¹², examplesinclude, but are not limited to, fluorine, chlorine, bromine, an iodineatom.

The alkoxy group may be an alkoxy group having 1 to 8 carbon atoms, suchas a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxygroup, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, at-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxygroup and an n-hexyloxy group.

The aryloxy group may be an aryloxy group having 6 to 12 carbon atoms,such as a phenoxy group.

The monoalkylamino group may be a monoalkylamino group having 1 to 8carbon atoms, such as a methylamino group, an ethylamino group, ann-propylamino group, an n-butylamino group and an n-hexylamino group.

The dialkylamino group may be a dialkylamino group having to 12 carbonatoms, such as a dimethylamino group, a diethylamino group, adi-n-propylamino group, a di-n-butylamino group and anN-methyl-N-cyclohexylamino group.

The alkylthio group may be an alkylthio group having 1 to 8 carbonatoms, such as a methylthio group, an ethylthio group, an n-propylthiogroup, an iso-propylthio group, an n-butylthio group, a t-butylthiogroup and an n-pentylthio group.

The arylthio group may be an arylthio group having 6 to 12 carbon atoms,such as a phenylthio group and a naphthylthio group.

In the general formula, the alkyl group as R¹ to R¹² may be any oflinear, branched, cyclic alkyl groups. It may be an alkyl group having 1to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propylgroup, an iso-propyl group, an n-butyl group, an iso-butyl group, asec-butyl group, a t-butyl group, an n-pentyl group, a 2-methylbutylgroup, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, ann-heptyl group, an n-octyl group and a 2-ethylhexyl group.

In the general formula, the aromatic ring group as R¹ to R¹² may be anaromatic hydrocarbon group or an aromatic heterocyclic group. Forexample, the aromatic hydrocarbon group may be an aromatic hydrocarbongroup having 6 to 12 carbon atoms, such as a phenyl group and a naphthylgroup. The aromatic heterocyclic group may be a pyrrolyl group, athienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group,an oxadiazolyl group, an imidazolyl group, a benzoxazolyl group, abenzothiazolyl group, a benzimidazolyl group, a benzofuranyl group or anindolyl group, for example.

In the general formula, the alkoxy group, aryloxy group, monoalkylaminogroup, dialkylamino group, alkylthio group, arylthio group, alkyl groupor aromatic ring group as R¹ to R¹² may contain a substituent.

In R¹ to R¹² of the general formula, the alkyl chain moiety of eachsubstituent may contain a substituent. The substituent may be thehalogen atom, the nitro group, the cyano group, the hydroxy group, theamino group, the carboxyl group, the sulfonic acid group, the alkoxygroup, the aryloxy group, the monoalkylamino group or the dialkylaminogroup, or it may be a trifluoromethyl group or an aromatic ring groupoptionally containing a substituent. That is, an aralkyl group such as abenzyl group, a benzyloxy group, an alkoxyalkoxy group or the like ispreferably used.

In R¹ to R¹² of the general formula, the aryl moiety of each substituentand the aromatic ring group may contain a substituent. The substituentmay be the halogen atom, the nitro group, the cyano group, the hydroxygroup, the amino group, the carboxyl group, the sulfonic acid group, thealkoxy group optionally containing a substituent, the aryloxy groupoptionally containing a substituent, the monoalkylamino group optionallycontaining a substituent, the dialkylamino group optionally containing asubstituent, the alkyl group optionally containing a substituent, and atrifluoromethyl group.

Or, R¹ and R², R³ and R⁴, R⁵ and R⁶, R⁷ and R⁸ may each independentlyform a ring which may contain an unsaturated bond. Examples of the ringinclude the case where 5 to 7-membered rings and condensed rings thereofare formed. As the ring, examples include, but are not limited to, thecase where a benzene ring is condensed to the pyrrole ring to which a R¹and R², R³ and R⁴, R⁵ and R⁶, R⁷ and R⁸ are each bound, the case where anaphthalene ring is condensed to the pyrrole ring, and the case where anazulene ring is condensed to the pyrrole ring. These formed ringstructures may further contain the substituent that the aromatic ringgroup may contain.

Also, as the ring, for example, R¹ and R², etc., may be linked to form aring by an alkylene chain which may contain a substituent such as—CH₂CH₂CH₂CH₂—, —CH₂CH₂CH(NO₂)CH₂—, —CH₂CH(CH₃)CH₂CH₂— and—CH₂CH(Cl)CH₂CH₂—.

X represents a carbon atom or a nitrogen atom. In the case of theporphyrin dye, X represents a carbon atom. In the case of thetetraazaporphyrin dye and the phthalocyanine dye, X represents anitrogen atom.

As the porphyrin dye, the tetraazaporphyrin dye and the phthalocyaninedye, examples include, but are not limited to, the following: thecompound 5-1 described in paragraph 0044 of Japanese Patent ApplicationLaid-Open (JP-A) No. 2006-73856 and the compound 6-1 described inparagraph 0045 thereof; the compound described in paragraphs 0038 to0042 of JP-A No. 2011-166062; the compound obtained by substituting themetal atom in the center of the compound described in paragraphs 0021 to0034 of JP-A No. 2012-63629 with two hydrogen atoms; and the compoundobtained by substituting the metal atom in the center of the compounddescribed in paragraphs 0083 to 0097 of JP-A No. 2010-18788 with twohydrogen atoms. This content is incorporated in the DESCRIPTION;however, the dyes are not limited to them.

The R¹ to R¹² and X of the general formula may be appropriately selectedfrom the viewpoint of obtaining desired absorption wavelength anddepending on absorption width, etc.

R¹ to R⁸ are each preferably the same, from the point of view that thesymmetry of the electronic state relating to the coloration of theporphyrin, tetraazaporphyrin and phthalocyanine dyes is increased, andthe dyes give narrow absorption with an acute, sharp half-width.

R¹ to R⁸ are each independently preferably a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, an aralkyl group or an aromatic ringgroup, especially from the viewpoint of sufficiently ensuring thesolubility of the dyes during the salt formation with theheteropolyoxometalate.

R⁹ to R¹² are each independently preferably the same, from the point ofview that the symmetry of the electronic state relating to thecoloration of the porphyrin dye is increased, and the dye gives narrowabsorption with an acute, sharp half-width.

R⁹ to R¹² are each independently preferably a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, an aralkyl group or an aromatic ringgroup, especially from the viewpoint of obtaining desired absorptionwavelength, sufficiently ensuring absorption width, and sufficientlyensuring the solubility of the dye during the salt formation with theheteropolyoxometalate.

The squarylium dye refers to a dye containing a 4-membered ring derivedfrom squaric acid.

The squarylium dye may be a compound represented by the followingformula (2-1), for example:

where A¹ and A² each independently represent an aromatic ring groupoptionally containing a substituent, or a group represented by thefollowing general formula (2-2):

where Z² represents a non-metallic atomic group forming anitrogen-containing heterocyclic ring; R²⁰ represents an alkyl group, analkenyl group or an aralkyl group; d represents 0 or 1; and the wavyline represents a linking moiety.

A¹ and A² of the general formula (2-1) each independently represent anaromatic ring group optionally containing a substituent, or a grouprepresented by the general formula (2-2).

The aromatic ring group may be an aromatic hydrocarbon group, that is,an aryl group, or may be an aromatic heterocyclic group, that is, aheteroaryl group.

The aromatic hydrocarbon group represented by A¹ and A² preferably has 6to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and still morepreferably 6 to 12 carbon atoms. The aromatic hydrocarbon group may be asingle ring or a condensed ring.

The aromatic heterocyclic group represented by A¹ and A² is preferably a5-membered ring or a 6-membered ring. Also, the aromatic heterocyclicgroup may be a single ring or a condensed ring, and it is preferably asingle ring or a condensed ring having a condensation number of from 2to 8, more preferably a single ring or a condensed ring having acondensation number of from 2 to 4, and still more preferably a singlering or a condensed ring having a condensation number of 2 or 3. As theheteroatom contained in the aromatic heterocyclic group, examplesinclude a nitrogen atom, an oxygen atom, a sulfur atom, and theheteroatom is preferably a nitrogen atom, a sulfur atom. The number ofthe heteroatom is preferably from 1 to 3, and more preferably 1 to 2.More specifically, examples include, but are not limited to, an aromaticheterocyclic group derived from a single ring, a polycyclic aromaticring such as a 5- or 6-membered ring containing at least one of anitrogen atom, an oxygen atom and a sulfur atom.

As the aromatic ring of the aromatic ring group, examples include, butare not limited to, a benzene ring, a naphthalene ring, a pentalenering, an indene ring, an azulene ring, a heptalene ring, an indecenering, a perylene ring, a pentacene ring, an acenaphthene ring, aphenanthrene ring, an anthracene ring, a naphthacene ring, a chrysenering, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrolering, a furan ring, a thiophene ring, an imidazole ring, an oxazolering, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidinering, a pyridazine ring, an indolizine ring, an indole ring, abenzofuran ring, a benzothiophene ring, an isobenzofuran ring, aquinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridinering, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, acarbazole ring, a phenanthridine ring, an acridine ring, aphenanthroline ring, a pyrrolo[2,1-b]benzothiazole ring, apyrrolo[2,1-a]isoquinoline ring, a thianthrene ring, a chromene ring, axanthene ring, a phenoxathiin ring, a phenothiazine ring, and aphenazine ring. The aromatic ring is preferably a benzene ring or anaphthalene ring.

The aromatic ring group as A¹ and A² may contain a substituent. When thearomatic ring group contain two or more substituents, the substituentsmay be the same or different.

As the substituent, examples include, but are not limited to, a halogenatom, a cyano group, a nitro group, an alkyl group, an alkenyl group, analkynyl group, an aromatic ring group, an aralkyl group, —OR¹⁰⁰,—COR¹⁰¹, —COOR¹⁰², —OCOR¹⁰³, —NR¹⁰⁴R¹⁰⁵, —NHCOR¹⁰⁶, —CONR¹⁰⁷R¹⁰⁸,—NHCONR¹⁰⁹R¹¹⁰, —NHCOOR¹¹¹, —SR¹¹², —SO₂R¹¹³, —SO²OR¹¹⁴, —NHSO₂R¹¹⁵,—SO₂R¹¹⁶R¹¹⁷ and —(R¹¹⁸O)_(n)R¹¹⁹. R¹⁰⁰ to R¹¹⁷ and R¹¹⁹ eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aromatic ring group or an aralkyl group.R¹¹⁸ each independently represents a divalent hydrocarbon group. WhenR¹⁰² of —COOR¹⁰² is hydrogen (that is, a carboxy group), the hydrogenatom may dissociate or may be in the state of salt. When R¹⁰⁴ of—SO₂OR¹⁰⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atommay dissociate or may be in the state of salt.

From the viewpoint of increasing solvent solubility, the divalenthydrocarbon group as R¹¹⁸ may be saturated or unsaturated, or it may beany of linear, branched, cyclic, or a combination of cyclic and linearor branched. From the viewpoint of increasing solvent solubility, thedivalent hydrocarbon group as R¹¹⁸ is preferably a linear or branchedhydrocarbon group. The divalent hydrocarbon group as R¹¹⁸ preferably has2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and still morepreferably 2 to 3 carbon atoms. Also, n may be from 1 to 18, and it ispreferably from 1 to 12, and more preferably from 1 to 6.

As the halogen atom, examples include a fluorine atom, a chlorine atom,a bromine atom, an iodine atom.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. Thealkyl group may be any of linear, branched, cyclic, and it is preferablylinear or branched.

The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. Thealkenyl group may be any of linear, branched, cyclic, and it ispreferably linear or branched.

The alkynyl group preferably has 2 to 40 carbon atoms, more preferably 2to 30 carbon atoms, and still more preferably 2 to 25 carbon atoms. Thealkynyl group may be any of linear, branched, cyclic, and it ispreferably linear or branched.

Of the aromatic ring groups, the aromatic hydrocarbon group preferablyhas 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, andstill more preferably 6 to 12 carbon atoms.

The alkyl moiety of the aralkyl group is the same as the alkyl group.The aryl moiety of the aralkyl group is the same as the aromatichydrocarbon group. The aralkyl group preferably has 7 to 40 carbonatoms, more preferably 7 to 30 carbon atoms, and still more preferably 7to 25 carbon atoms.

Of the aromatic ring groups, the aromatic heterocyclic group ispreferably a single ring or a condensed ring, more preferably a singlering or a condensed ring having a condensation number of from 2 to 8,and still more preferably a single ring or a condensed ring having acondensation number of from 2 to 4. The number of the heteroatomconstituting the ring of the aromatic heterocyclic group, is preferablyfrom 1 to 3. The heteroatom constituting the ring of the aromaticheterocyclic group, is preferably a nitrogen atom, an oxygen atom or asulfur atom. The aromatic heterocyclic group is preferably a 5- or6-membered ring. The number of the carbon atoms constituting the ring ofthe aromatic heterocyclic group, is preferably from 3 to 30, morepreferably from 3 to 18, and still more preferably from 3 to 12.

The alkyl group, the alkenyl group, the alkynyl group, the aralkylgroup, the aromatic ring group may contain a substituent or may beunsubstituted. As the substituent, examples include the above-describedsubstituents.

In the group represented by the general formula (2-2) which isrepresented by A¹ and A², R²⁰ represents an alkyl group, an alkenylgroup or an aralkyl group, and it is preferably an alkyl group.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1to 20 carbon atoms, still more preferably 1 to 12 carbon atoms, andparticularly preferably 2 to 8 carbon atoms.

The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms.

The alkyl group and the alkenyl group may be any of linear, branched,cyclic. They are preferably linear or branched.

The aralkyl group preferably has 7 to 30 carbon atoms, and morepreferably 7 to 20 carbon atoms.

In the general formula (2-2), the nitrogen-containing heterocyclic ringformed by Z¹ is preferably a 5-membered ring or a 6-membered ring. Thenitrogen-containing heterocyclic ring is preferably a single ring or acondensed ring, more preferably a single ring or a condensed ring havinga condensation number of from 2 to 8, still more preferably a singlering or a condensed ring having a condensation number of from 2 to 4,and particularly preferably a condensed ring having a condensationnumber of 2 or 3. In addition to a nitrogen atom, thenitrogen-containing heterocyclic ring may contain a sulfur atom. Thenitrogen-containing heterocyclic ring may contain a substituent. As thesubstituent, examples include the above-described substituents. Forexample, the substituent is preferably a halogen atom, an alkyl group, ahydroxy group, an amino group, an acylamino group, and more preferably ahalogen atom and an alkyl group. The halogen atom is preferably achlorine atom. The alkyl group preferably has 1 to 30 carbon atoms, morepreferably 1 to 20 carbon atoms, and still more preferably 1 to carbonatoms. The alkyl group is preferably linear or branched.

In the general formula (2-1), the cation is delocalized and present asshown below.

For the details of the formulae (2-1) and (2-2), the description inparagraphs 0055 to 0071 of JP-A No. 2017-181705 and paragraphs 0020 to0049 of JP-A No. 2011-208101 can be taken into consideration, and theyare incorporated in the DESCRIPTION.

The squarylium dye may be a structure having two or more 4-memberedrings derived from squaric acid per molecule, such as a structure thatany one of A¹ and A² of the compound represented by the formula (2-1) isbound to any one of A¹ and A² of another compound represented by theformula (2-1) by a linking group. The squarylium dye of the structurehaving two or more 4-membered rings derived from squaric acid permolecule, may be the compound described in paragraphs 0018 to 0019, 0048to 0093 of JP-A No. 2009-40860.

As the squarylium dye, examples include, but are not limited to, thefollowing compounds. As the squarylium dye, examples also include thecompound described in paragraphs 0044 to 0049 of JP-A No. 2011-208101and the compound described in paragraphs 0018 to 0019, 0048 to 0110 ofJP-A No. 2009-40860, and the contents thereof are incorporated in theDESCRIPTION.

In the present invention, from the viewpoint of narrowing the half-widthof an absorption spectrum or transmission spectrum, the squarylium dyeis particularly preferably a compound represented by the followinggeneral formula (3-1):

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent organicgroup; Z⁰ represents a group which can be converted to an organic cationgroup, or an organic cation group; e represents an integer of from 1 to4; and when e is 2 or more, a plurality of Ys and a plurality of Z⁰ smay be each the same or different.

The aromatic ring group optionally containing a substituent as X¹ and X²of the general formula (3-1) may be the same as the aromatic ring groupoptionally containing a substituent as A¹ and A² of the general formula(2-1).

From the viewpoint of increasing solvent solubility, X¹ and X²preferably contain at least one substituent selected from the groupconsisting of —(R¹¹⁸O)_(n)R¹¹⁹, an aralkyl group, —OR¹⁰⁰, —COR¹⁰¹,—COOR¹⁰², —OCOR¹⁰³, —NR¹⁰⁴R¹⁰⁵, —NHCOR¹⁰⁶, —CONR¹⁰⁷R¹⁰⁸, —NHCONR¹⁰⁹R¹¹⁰,—NHCOOR¹¹¹, —SR¹¹², —SO₂R¹¹³, —SO₂OR¹¹⁴, —NHSO₂R¹¹⁵ and —SO₂NR¹¹⁶R¹¹⁷.The —(R¹¹⁸O)_(n)R¹¹⁹, —OR¹⁰⁰, —COR¹⁰¹, —COOR¹⁰², —OCOR¹⁰³, —NR¹⁰⁴R¹⁰⁵,—NHCOR¹⁰⁶, —CONR¹⁰⁷R¹⁰⁸, —NHCONR¹⁰⁹R¹¹⁰, —NHCOOR¹¹¹, —SR¹¹², —SO₂R¹¹³,—SO₂OR¹¹⁴, —NHSO₂R¹¹⁵ or —SO₂NR¹¹⁶R¹¹⁷ may be the same as thesubstituent described in A¹ and A².

From the viewpoint of the ease of giving a dye framework havingabsorption in the visible range (380 nm to 750 nm), preferred examplesof X¹ and X² include, but are not limited to, the following chemicalformulae (x-1) to (x-11):

where R, R′ and R″ each independently represent a hydrogen atom, analkyl group having 1 to 12 carbon atoms or —(CH₂CH₂O)_(n′)—R¹²⁰; and n′is from 2 to 12; R¹²⁰ represents a hydrocarbon group having 1 to 4carbon atoms. In the formulae, * indicates a binding position to a4-membered ring derived from squaric acid or Y.

From the viewpoint of increasing solvent solubility, at least one of R,R′ and R″ of the chemical formulae (x-1) to (x-11) preferably represents—(CH₂CH₂O)_(n′)—R¹²⁰. In —(CH₂CH₂O)_(n′)—R¹²⁰, n′ is preferably from 1to 8, and more preferably from 1 to 6. R¹²⁰ is preferably a methylgroup, an ethyl group, an n-propyl group, an i-propyl group or ann-butyl group.

In the general formula (3-1), Y represents a divalent organic group andfunctions as a linking group between at least one of X¹ and X² of thesquarylium dye moiety and Z⁰ which is a group which can be converted toa cation group, or an organic cation group.

As the divalent organic group as Y, examples include a divalenthydrocarbon group optionally containing a heteroatom, and a divalenthydrocarbon group optionally containing O, S, N in the carbon chain. Asthe divalent organic group as Y, examples include, but are not limitedto, a divalent hydrocarbon group and a divalent group which is acombination of a divalent hydrocarbon group and —CONH—, —COO—, —O—, —S—,etc.

The divalent hydrocarbon group may be any of saturated or unsaturated.Also, it may be linear, branched, cyclic, or a combination of cyclic andlinear or branched.

The divalent hydrocarbon group preferably has 1 to 30 carbon atoms, morepreferably 1 to 2 carbon atoms, still more preferably 1 to 15 carbonatoms, even more preferably 1 to 12 carbon atoms, and particularlypreferably 2 to 8 carbon atoms.

From the viewpoint of optical stability, the divalent organic group as Yis preferably a divalent hydrocarbon group.

When the squarylium dye moiety relating to coloration and the cationgroup are electronically independent, the spread of electrondistribution relating to coloration can be suppressed, and narrowabsorption with an acute, sharp half-width is given. From thisviewpoint, Y is preferably a hydrocarbon group that the carbon atomdirectly bound to X′ or X² does not have a n bond, more preferably analiphatic hydrocarbon group containing a saturated aliphatic hydrocarbongroup at a terminal directly bound to X′ or X² or an aromatichydrocarbon group containing a saturated aliphatic hydrocarbon group ata terminal directly bound to X′ or X², and still more preferably analiphatic saturated hydrocarbon group.

As Y which is preferred from the viewpoint of being inactive againstoxidation, reduction, or hydrolysis reaction which can cause dyedeterioration, and chemically stably linking Z⁰ to X¹ or X², examplesinclude, but are not limited to, the following chemical formulae (y-1)to (y-6).

Of them, Y is preferably (y-1), (y-3), (y-5) or (y-6), and morepreferably (y-1), (y-3) or (y-5), from the viewpoint of giving narrowabsorption with an acute, sharp half-width.

In the formulae, * indicates a binding position between Z⁰ and one of X¹and X².

In the general formula (3-1), Z⁰ is a group which can be converted to anorganic cation group (Z⁺), or an organic cation group.

As the group which can be converted to an organic cation group (Z⁺) asZ⁰, examples include, but are not limited to, a monovalentnitrogen-containing compound group which can be an onium, a monovalentsulfur-containing compound group which can be an onium, and a monovalentphosphorus-containing compound group which can be an onium. The organiccation group (Z⁺) is not limited to a protonated onium, and it may be anonium substituted by a hydrocarbon group in place of a proton.

As the nitrogen-containing compound which can be an onium, examplesinclude, but are not limited to, tertiary amine, piperidine,pyrrolidine, pyridine, imidazoline and morpholine.

As the sulfur-containing compound which can be an onium, examplesinclude, but are not limited to, thiol and thioether.

As the phosphorus-containing compound which can be an onium, examplesinclude, but are not limited to, phosphine.

As the organic cation group (Z⁺) as Z⁰, examples include an oniumstructure derived from the group (Z⁰) which can be converted to thecation group. As the structure, examples include, but are not limitedto, an ammonium cation such as a tetraalkylammonium cation and atrialkylammonium cation, a piperidinium cation, a pyrrolidinium cation,a pyridinium cation, an imidazolium cation, a morpholium and a sulfoniumcation such as a trialkylsulfonium cation, and a phosphonium cation suchas a tetraalkylphosphonium cation.

From the viewpoint of the ease of cationization by protonation andavailability of relatively inexpensive raw materials, a tertiary aminogroup, a pyridyl group, an imidazolyl group, etc., are preferably usedas Z⁰.

From the point of view that the formed onium is stably present as acation, preferred examples of Z⁰ include, but are not limited to, thefollowing chemical formulae (z-1) to (z-9):

where R and R′ each independently represent a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms or —(CH₂CH₂O)_(n′)—R¹²⁰; and n′ isfrom 2 to 12; and R¹²⁰ represents a hydrocarbon group having 1 to 4carbon atoms. In the formulae, * indicates a binding position to Y.

Also, —(CH₂CH₂O)_(n′)—R¹²⁰ in the chemical formulae (z-1) to (z-9) maybe the same as —(CH₂CH₂O)_(n′)—R¹²⁰ in the above-mentioned (x-1) to(x-11).

Also, e represents an integer of from 1 to 4. From the viewpoint offorming continuous ion pairs and increasing the molecular weight of theion pair association for higher resistance to heat and light, e ispreferably from 2 to 4, more preferably from 2 to 3, and still morepreferably 2.

When e is 2 or more, a plurality of Ys and a plurality of Z⁰ s may beeach the same or different.

From the point of view that the symmetry of the electronic staterelating to the coloration of the squarylium dye is increased, and thedye gives narrow absorption with an acute, sharp half-width, X² and X²,a plurality of Ys and a plurality of Z⁰ s are each independentlypreferably the same.

As the compound represented by the general formula (3-1), examplesinclude, but are not limited to, the following compounds.

TABLE 1 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side)  (C1) z−1 y−1 x−1 x−1 y−1 z−1  (C2) z−2 y−1 x−1 x−1 y−1 z−2  (C3)z−3 y−1 x−1 x−1 y−1 z−3  (C4) z−4 y−1 x−1 x−1 y−1 z−4  (C5) z−5 y−1 x−1x−1 y−1 z−5  (C6) z−6 y−1 x−1 x−1 y−1 z−6  (C7) z−7 y−1 x−1 x−1 y−1 z−7 (C8) z−8 y−1 x−1 x−1 y−1 z−8  (C9) z−9 y−1 x−1 x−1 y−1 z−9 (C10) z−1y−2 x−1 x−1 y−2 z−1 (C11) z−2 y−2 x−1 x−1 y−2 z−2 (C12) z−3 y−2 x−1 x−1y−2 z−3 (C13) z−4 y−2 x−1 x−1 y−2 z−4 (C14) z−5 y−2 x−1 x−1 y−2 z−5(C15) z−6 y−2 x−1 x−1 y−2 z−6 (C16) z−7 y−2 x−1 x−1 y−2 z−7 (C17) z−8y−2 x−1 x−1 y−2 z−8 (C18) z−9 y−2 x−1 x−1 y−2 z−9 (C19) z−1 y−3 x−1 x−1y−3 z−1 (C20) z−2 y−3 x−1 x−1 y−3 z−2 (C21) z−3 y−3 x−1 x−1 y−3 z−3(C22) z−4 y−3 x−1 x−1 y−3 z−4 (C23) z−5 y−3 x−1 x−1 y−3 z−5 (C24) z−6y−3 x−1 x−1 y−3 z−6 (C25) z−7 y−3 x−1 x−1 y−3 z−7 (C26) z−8 y−3 x−1 x−1y−3 z−8 (C27) z−9 y−3 x−1 x−1 y−3 z−9 (C28) z−1 y−4 x−1 x−1 y−4 z−1(C29) z−2 y−4 x−1 x−1 y−4 z−2 (C30) z−3 y−4 x−1 x−1 y−4 z−3 (C31) z−4y−4 x−1 x−1 y−4 z−4 (C32) z−5 y−4 x−1 x−1 y−4 z−5 (C33) z−6 y−4 x−1 x−1y−4 z−6 (C34) z−7 y−4 x−1 x−1 y−4 z−7 (C35) z−8 y−4 x−1 x−1 y−4 z−8(C36) z−9 y−4 x−1 x−1 y−4 z−9 (C37) z−1 y−5 x−1 x−1 y−5 z−1 (C38) z−2y−5 x−1 x−1 y−5 z−2 (C39) z−3 y−5 x−1 x−1 y−5 z−3 (C40) z−4 y−5 x−1 x−1y−5 z−4 (C41) z−5 y−5 x−1 x−1 y−5 z−5 (C42) z−6 y−5 x−1 x−1 y−5 z−6(C43) z−7 y−5 x−1 x−1 y−5 z−7 (C44) z−8 y−5 x−1 x−1 y−5 z−8 (C45) z−9y−5 x−1 x−1 y−5 z−9

TABLE 2 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side) (C46) z−1 y−6 x−1 x−1 y−6 z−1 (C47) z−2 y−6 x−1 x−1 y−6 z−2 (C48)z−3 y−6 x−1 x−1 y−6 z−3 (C49) z−4 y−6 x−1 x−1 y−6 z−4 (C50) z−5 y−6 x−1x−1 y−6 z−5 (C51) z−6 y−6 x−1 x−1 y−6 z−6 (C52) z−7 y−6 x−1 x−1 y−6 z−7(C53) z−8 y−6 x−1 x−1 y−6 z−8 (C54) z−9 y−6 x−1 x−1 y−6 z−9 (C55) z−1y−1 x−2 x−2 y−1 z−1 (C56) z−2 y−1 x−2 x−2 y−1 z−2 (C57) z−3 y−1 x−2 x−2y−1 z−3 (C58) z−4 y−1 x−2 x−2 y−1 z−4 (C59) z−5 y−1 x−2 x−2 y−1 z−5(C60) z−6 y−1 x−2 x−2 y−1 z−6 (C61) z−7 y−1 x−2 x−2 y−1 z−7 (C62) z−8y−1 x−2 x−2 y−1 z−8 (C63) z−9 y−1 x−2 x−2 y−1 z−9 (C64) z−1 y−2 x−2 x−2y−2 z−1 (C65) z−2 y−2 x−2 x−2 y−2 z−2 (C66) z−3 y−2 x−2 x−2 y−2 z−3(C67) z−4 y−2 x−2 x−2 y−2 z−4 (C68) z−5 y−2 x−2 x−2 y−2 z−5 (C69) z−6y−2 x−2 x−2 y−2 z−6 (C70) z−7 y−2 x−2 x−2 y−2 z−7 (C71) z−8 y−2 x−2 x−2y−2 z−8 (C72) z−9 y−2 x−2 x−2 y−2 z−9 (C73) z−1 y−3 x−2 x−2 y−3 z−1(C74) z−2 y−3 x−2 x−2 y−3 z−2 (C75) z−3 y−3 x−2 x−2 y−3 z−3 (C76) z−4y−3 x−2 x−2 y−3 z−4 (C77) z−5 y−3 x−2 x−2 y−3 z−5 (C78) z−6 y−3 x−2 x−2y−3 z−6 (C79) z−7 y−3 x−2 x−2 y−3 z−7 (C80) z−8 y−3 x−2 x−2 y−3 z−8(C81) z−9 y−3 x−2 x−2 y−3 z−9 (C82) z−1 y−4 x−2 x−2 y−4 z−1 (C83) z−2y−4 x−2 x−2 y−4 z−2 (C84) z−3 y−4 x−2 x−2 y−4 z−3 (C85) z−4 y−4 x−2 x−2y−4 z−4 (C86) z−5 y−4 x−2 x−2 y−4 z−5 (C87) z−6 y−4 x−2 x−2 y−4 z−6(C88) z−7 y−4 x−2 x−2 y−4 z−7 (C89) z−8 y−4 x−2 x−2 y−4 z−8 (C90) z−9y−4 x−2 x−2 y−4 z−9

TABLE 3 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side)  (C91) z−1 y−5 x−2 x−2 y−5 z−1  (C92) z−2 y−5 x−2 x−2 y−5 z−2 (C93) z−3 y−5 x−2 x−2 y−5 z−3  (C94) z−4 y−5 x−2 x−2 y−5 z−4  (C95) z−5y−5 x−2 x−2 y−5 z−5  (C96) z−6 y−5 x−2 x−2 y−5 z−6  (C97) z−7 y−5 x−2x−2 y−5 z−7  (C98) z−8 y−5 x−2 x−2 y−5 z−8  (C99) z−9 y−5 x−2 x−2 y−5z−9 (C100) z−1 y−6 x−2 x−2 y−6 z−1 (C101) z−2 y−6 x−2 x−2 y−6 z−2 (C102)z−3 y−6 x−2 x−2 y−6 z−3 (C103) z−4 y−6 x−2 x−2 y−6 z−4 (C104) z−5 y−6x−2 x−2 y−6 z−5 (C105) z−6 y−6 x−2 x−2 y−6 z−6 (C106) z−7 y−6 x−2 x−2y−6 z−7 (C107) z−8 y−6 x−2 x−2 y−6 z−8 (C108) z−9 y−6 x−2 x−2 y−6 z−9(C109) z−1 y−1 x−3 x−3 y−1 z−1 (C110) z−2 y−1 x−3 x−3 y−1 z−2 (C111) z−5y−1 x−3 x−3 y−1 z−5 (C112) z−8 y−1 x−3 x−3 y−1 z−8 (C113) z−1 y−3 x−3x−3 y−3 z−1 (C114) z−2 y−3 x−3 x−3 y−3 z−2 (C115) z−5 y−3 x−3 x−3 y−3z−5 (C116) z−8 y−3 x−3 x−3 y−3 z−8 (C117) z−1 y−5 x−3 x−3 y−5 z−1 (C118)z−2 y−5 x−3 x−3 y−5 z−2 (C119) z−5 y−5 x−3 x−3 y−5 z−5 (C120) z−8 y−5x−3 x−3 y−5 z−8 (C121) z−1 y−1 x−4 x−4 y−1 z−1 (C122) z−2 y−1 x−4 x−4y−1 z−2 (C123) z−5 y−1 x−4 x−4 y−1 z−5 (C124) z−8 y−1 x−4 x−4 y−1 z−8(C125) z−1 y−3 x−4 x−4 y−3 z−1 (C126) z−2 y−3 x−4 x−4 y−3 z−2 (C127) z−5y−3 x−4 x−4 y−3 z−5 (C128) z−8 y−3 x−4 x−4 y−3 z−8 (C129) z−1 y−5 x−4x−4 y−5 z−1 (C130) z−2 y−5 x−4 x−4 y−5 z−2 (C131) z−5 y−5 x−4 x−4 y−5z−5 (C132) z−8 y−5 x−4 x−4 y−5 z−8 (C133) z−1 y−1 x−5 x−5 y−1 z−1 (C134)z−2 y−1 x−5 x−5 y−1 z−2 (C135) z−5 y−1 x−5 x−5 y−1 z−5

TABLE 4 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side) (C136) z−8 y−1 x−5 x−5 y−1 z−8 (C137) z−1 y−3 x−5 x−5 y−3 z−1(C138) z−2 y−3 x−5 x−5 y−3 z−2 (C139) z−5 y−3 x−5 x−5 y−3 z−5 (C140) z−8y−3 x−5 x−5 y−3 z−8 (C141) z−1 y−5 x−5 x−5 y−5 z−1 (C142) z−2 y−5 x−5x−5 y−5 z−2 (C143) z−5 y−5 x−5 x−5 y−5 z−5 (C144) z−8 y−5 x−5 x−5 y−5z−8 (C145) z−1 y−1 x−6 x−6 y−1 z−1 (C146) z−2 y−1 x−6 x−6 y−1 z−2 (C147)z−5 y−1 x−6 x−6 y−1 z−5 (C148) z−8 y−1 x−6 x−6 y−1 z−8 (C149) z−1 y−3x−6 x−6 y−3 z−1 (C150) z−2 y−3 x−6 x−6 y−3 z−2 (C151) z−5 y−3 x−6 x−6y−3 z−5 (C152) z−8 y−3 x−6 x−6 y−3 z−8 (C153) z−1 y−5 x−6 x−6 y−5 z−1(C154) z−2 y−5 x−6 x−6 y−5 z−2 (C155) z−5 y−5 x−6 x−6 y−5 z−5 (C156) z−8y−5 x−6 x−6 y−5 z−8 (C157) z−1 y−1 x−7 x−7 y−1 z−1 (C158) z−2 y−1 x−7x−7 y−1 z−2 (C159) z−5 y−1 x−7 x−7 y−1 z−5 (C160) z−8 y−1 x−7 x−7 y−1z−8 (C161) z−1 y−3 x−7 x−7 y−3 z−1 (C162) z−2 y−3 x−7 x−7 y−3 z−2 (C163)z−5 y−3 x−7 x−7 y−3 z−5 (C164) z−8 y−3 x−7 x−7 y−3 z−8 (C165) z−1 y−5x−7 x−7 y−5 z−1 (C166) z−2 y−5 x−7 x−7 y−5 z−2 (C167) z−5 y−5 x−7 x−7y−5 z−5 (C168) z−8 y−5 x−7 x−7 y−5 z−8 (C169) z−1 y−1 x−8 x−8 y−1 z−1(C170) z−2 y−1 x−8 x−8 y−1 z−2 (C171) z−5 y−1 x−8 x−8 y−1 z−5 (C172) z−8y−1 x−8 x−8 y−1 z−8 (C173) z−1 y−3 x−8 x−8 y−3 z−1 (C174) z−2 y−3 x−8x−8 y−3 z−2 (C175) z−5 y−3 x−8 x−8 y−3 z−5 (C176) z−8 y−3 x−8 x−8 y−3z−8 (C177) z−1 y−5 x−8 x−8 y−5 z−1 (C178) z−2 y−5 x−8 x−8 y−5 z−2 (C179)z−5 y−5 x−8 x−8 y−5 z−5 (C180) z−8 y−5 x−8 x−8 y−5 z−8

TABLE 5 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side) (C181) z−1 y−1 x−1  x−9  y−1 z−1 (C182) z−2 y−1 x−9  x−9  y−1 z−2(C183) z−5 y−1 x−9  x−9  y−1 z−5 (C184) z−8 y−1 x−9  x−9  y−1 z−8 (C185)z−1 y−3 x−9  x−9  y−3 z−1 (C186) z−2 y−3 x−9  x−9  y−3 z−2 (C187) z−5y−3 x−9  x−9  y−3 z−5 (C188) z−8 y−3 x−9  x−9  y−3 z−8 (C189) z−1 y−5x−9  x−9  y−5 z−1 (C190) z−2 y−5 x−9  x−9  y−5 z−2 (C191) z−5 y−5 x−9 x−9  y−5 z−5 (C192) z−8 y−5 x−9  x−9  y−5 z−8 (C193) z−1 y−1 x−10 x−10y−1 z−1 (C194) z−2 y−1 x−10 x−10 y−1 z−2 (C195) z−5 y−1 x−10 x−10 y−1z−5 (C196) z−8 y−1 x−10 x−10 y−1 z−8 (C197) z−1 y−3 x−10 x−10 y−3 z−1(C198) z−2 y−3 x−10 x−10 y−3 z−2 (C199) z−5 y−3 x−10 x−10 y−3 z−5 (C200)z−8 y−3 x−10 x−10 y−3 z−8 (C201) z−1 y−5 x−10 x−10 y−5 z−1 (C202) z−2y−5 x−10 x−10 y−5 z−2 (C203) z−5 y−5 x−10 x−10 y−5 z−5 (C204) z−8 y−5x−10 x−10 y−5 z−8 (C205) z−1 y−1 x−11 x−11 y−1 z−1 (C206) z−2 y−1 x−11x−11 y−1 z−2 (C207) z−5 y−1 x−11 x−11 y−1 z−5 (C208) z−8 y−1 x−11 x−11y−1 z−8 (C209) z−1 y−3 x−11 x−11 y−3 z−1 (C210) z−2 y−3 x−11 x−11 y−3z−2 (C211) z−5 y−3 x−11 x−11 y−3 z−5 (C212) z−8 y−3 x−11 x−11 y−3 z−8(C213) z−1 y−5 x−11 x−11 y−5 z−1 (C214) z−2 y−5 x−11 x−11 y−5 z−2 (C215)z−5 y−5 x−11 x−11 y−5 z−5 (C216) z−8 y−5 x−11 x−11 y−5 z−8 (C217) z−1y−1 x−1  x−10 y−1 z−1 (C218) z−2 y−1 x−1  x−10 y−1 z−2 (C219) z−5 y−1x−1  x−10 y−1 z−5 (C220) z−8 y−1 x−1  x−10 y−1 z−8 (C221) z−1 y−3 x−1 x−10 y−3 z−1 (C222) z−2 y−3 x−1  x−10 y−3 z−2 (C223) z−5 y−3 x−1  x−10y−3 z−5 (C224) z−8 y−3 x−1  x−10 y−3 z−8

TABLE 6 Com- Z⁰ (X¹ Y (X¹ Y (X² Z⁰ (X² pound side) side) X¹ X² side)side) (C225) z−1 y−5 x−1 x−10 y−5 z−1 (C226) z−2 y−5 x−1 x−10 y−5 z−2(C227) z−3 y−5 x−1 x−10 y−5 z−5 (C228) z−4 y−5 x−1 x−10 y−5 z−8 (C229)z−5 y−1 x−1 x−11 y−1 z−1 (C230) z−6 y−1 x−1 x−11 y−1 z−2 (C231) z−7 y−1x−1 x−11 y−1 z−5 (C232) z−8 y−1 x−1 x−11 y−1 z−8 (C233) z−9 y−3 x−1 x−11y−3 z−1 (C234) z−1 y−3 x−1 x−11 y−3 z−2 (C235) z−2 y−3 x−1 x−11 y−3 z−5(C236) z−3 y−3 x−1 x−11 y−3 z−8 (C237) z−4 y−5 x−1 x−11 y−5 z−1 (C238)z−5 y−5 x−1 x−11 y−5 z−2 (C239) z−6 y−5 x−1 x−11 y−5 z−5 (C240) z−7 y−5x−1 x−11 y−5 z−8

In the color material used in the disclosed embodiments, the organic dyeforms the salt-forming compound with the heteropolyoxometalate having anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

The organic dye is cationized by the proton (H⁺) of theheteropolyoxometalate or other cation, and as the counter anion thereof,the anion of the above-specified heteropolyoxometalate is used. Byusing, as the counter anion, such a heteropolyoxometalate anion that theoxidation-reduction potential is larger than the specific value, theheteropolyoxometalate having a property of being easily reduced absorbsthe energy which is generated when the organic dye is photoexcited andreturns to the ground state, whereby the singlet oxygen generation canbe suppressed during light irradiation, and the light resistance of thecolor material is further increased.

The heteropolyoxometalate anion is represented by the formula(L_(l)M_(m)O_(n))^(a−) (where a is a number of 2 or more). In the ionicformula, L represents heteroatom; M represents polyatom, O representsoxygen atom; and l, m and n represent the composition ratio of eachatom. As the polyatom M, examples include, but are not limited to, Mo(molybdenum), W (tungsten), V (vanadium), Ti (titanium) and Nb(niobium). Two or more kinds of transition metal atoms may be containedin the polyatom M.

The heteroatom L is not particularly limited. As the heteroatom L,examples include, but are not limited to, Si, P, As, S, Fe and Co. Acounter cation such as Na⁺ and H⁺ may be contained in a part thereof.

In the disclosed embodiments, as the heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode, examples include, but are not limitedto, H₄SiMo₁₂O₄₀ (−0.232 V) H₃PW₆Mo₆O₄₀ (−0.197 V) H₃PW₃Mo₉O₄₀ (−0.153 V)H₃PMo₁₂O₄₀ (−0.082 V), H₆PW₉V₃O₄₀ (0.045 V), H₅PW₁₀V₂O₄₀ (0.050 V),H₆PMo₉V₃O₄₀ (0.168 V) H₃AsMo₁₂O₄₀ (0.183 V) H₄PW₁₁V₁O₄₀ (0.224 V)H₅PMo₁₀V₂O₄₀ (0.233 V) and H₄PMo₁₁V₁O₄₀ (0.261 V).

The oxidation-reduction potential specified in the disclosed embodimentsrefers to a value obtained by measuring a heteropolyoxometalate aqueoussolution with the silver/silver chloride standard electrode (a KClsaturated aqueous solution) using platinum as the working electrode. Asthe heteropolyoxometalate aqueous solution, an aqueous solution obtainedby dissolving 1 mM heteropolyoxometalate in a 0.5 M sodium sulfateelectrolyte aqueous solution, can be used.

For the oxidation-reduction potential of the heteropolyoxometalate onthe above-described measurement condition, the values of theoxidation-reduction potentials (V) in FIG. 9 of Journal of MoleculerCatalysis A: Chemical 212 (2004) 229-236, can be used as reference. Theabove-described values in parentheses are the values described in thereference.

In the disclosed embodiments, for the heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode, the oxidation-reduction potential ispreferably 0 V or more relative to the silver/silver chloride electrode,from the viewpoint of increasing the light resistance.

In the disclosed embodiments, the heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode, preferably contains vanadium, from thepoint of view that the oxidation-reduction potential increases and,especially, the light resistance increases.

In the color material, as the heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode, one kind of heteropolyoxometalate maybe used solely, or a combination of two or more kinds ofheteropolyoxometalates may be used.

In the color material used in the disclosed embodiments, from theviewpoint of narrowing the half-width of an absorption spectrum ortransmission spectrum, the salt-forming compound is preferably thesalt-forming compound represented by the following general formula (1),for example:

where R¹ to R¹² each independently represent a hydrogen atom, a halogenatom, a nitro group, a cyano group, a hydroxy group, an amino group, acarboxyl group, a sulfonic acid group, an alkoxy group optionallycontaining a substituent, an aryloxy group optionally containing asubstituent, a monoalkylamino group optionally containing a substituent,a dialkylamino group optionally containing a substituent, an alkylthiogroup optionally containing a substituent, an arylthio group optionallycontaining a substituent, an alkyl group optionally containing asubstituent or an aromatic ring group optionally containing asubstituent; X represents a carbon atom or a nitrogen atom; and when Xis a nitrogen atom, R⁹ to R¹² are not present; or R¹ and R², R³ and R⁴,R⁵ and R⁶, R⁷ and R⁸ may each independently form a ring, and the ringmay contain an unsaturated bond;

A^(c−) represents a heteropolyoxometalate anion which is a c-valentanion and which has an oxidation-reduction potential larger than −0.3 Vrelative to the silver/silver chloride electrode; a, b and c are each aninteger of 2 or more; d is an integer of 1 or more; and the salt-formingcompound is a normal salt that axb=cx d.

R¹ to R¹² of the general formula (1) will not be described here, sincethey may be the same as R¹ to R¹² of the general formula (1-1).

Since b is an integer of 2 or more, two or more compounds represented bythe general formula (1-1) are contained in the salt-forming compound ofthe general formula (1). In the salt-forming compound, as the containedtwo or more compounds represented by the general formula (1-1), one kindof compound may be solely, or a combination of two or more kinds ofcompounds may be used. Accordingly, a plurality of R¹s, a plurality ofR²s, a plurality of R³s, a plurality of R⁴s, a plurality of R⁵s, aplurality of R⁶s, a plurality of R⁷s, a plurality of R⁸s, a plurality ofR⁹s, a plurality of R¹⁰s, a plurality of R¹¹s and a plurality of R¹²smay be each the same or different. From the viewpoint of suppressing thebroadening of an absorption peak due to the interference of the dyes, inthe salt-forming compound, the contained two or more compoundsrepresented by the general formula (1-1) are preferably one kind ofcompounds, and a plurality of R¹s, a plurality of R²s, a plurality ofR³s, a plurality of R⁴s, a plurality of R⁵s, a plurality of R⁶s, aplurality of R⁷s, a plurality of R⁸s, a plurality of R⁹s, a plurality ofR¹⁰s, a plurality of R¹¹s and a plurality of R¹²s are each preferablythe same.

Also, A^(c−) is an anion of the heteropolyoxometalate. As A^(c−),examples include, but are not limited to, [SiM₁₂O₄₀]⁴⁻, [PW₉Mo₃O₄₀]³⁻,[PW₆Mo₆O₄₀]³⁻, [PW₃Mo₉O₄₀]³⁻, [PMo₁₂O₄₀]³⁻, [PW₉V₃O₄₀]⁶⁻, [PW₁₀V₂O₄₀]⁵⁻,[PMo₉V₃O₄₀]⁶⁻, [AsMo₁₂O₄₀]³⁻, [PW₁₁V₁O₄₀]⁴⁻, [PMo₁₀V₂O₄₀]⁵⁻ and[PMo₁₁V₁O₄₀]⁴⁻.

For the heteropolyoxometalate which has an oxidation-reduction potentiallarger than −0.3 V relative to the silver/silver chloride electrode, theoxidation-reduction potential is preferably 0 V or more relative to thesilver/silver chloride electrode, from the viewpoint of increasing thelight resistance.

The heteropolyoxometalate which has an oxidation-reduction potentiallarger than −0.3 V relative to the silver/silver chloride electrode,preferably contains vanadium, from the point of view that theoxidation-reduction potential increases and, especially, the lightresistance increases.

A plurality of A^(c−) s may be each the same or different.

In the color material used in the disclosed embodiments, thesalt-forming compound is preferably the salt-forming compoundrepresented by the following general formula (3), for example:

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent organicgroup; Z⁺ represents an organic cation group; e represents an integer offrom 1 to 4; and when e is 2 or more, a plurality of Ys and a pluralityof Z⁺s may be each the same or different;

A^(c−) represents a heteropolyoxometalate anion which is a c-valentanion and which has an oxidation-reduction potential larger than −0.3 Vrelative to the silver/silver chloride electrode; f and c are each aninteger of 2 or more; g is an integer of 1 or more; and the salt-formingcompound is a normal salt that fxe=cx g.

X¹, X², Y and e of the general formula (3) will not be described here,since they may be the same as X¹, X², Y and e of the general formula(3-1).

Z⁺ of the general formula (3) represents an organic cation group.

As Z⁺ (an organic cation group), examples include an onium structurederived from the group (Z⁰) which can be converted to the cation group,and Z⁺ (the organic cation group) may be the same as that described inZ⁰ of the general formula (3-1). From the viewpoint of availability ofraw materials, Z⁺ is preferably a protonated, nitrogen-containingorganic cation.

Since f is 2 or more, two X's and two X²s are contained. A plurality ofX's and a plurality of X²s may be each the same or different. From thepoint of view that the symmetry of the components or association statesof the associations formed by the ion pairs is increased, and a sharperabsorption spectrum or transmission spectrum is obtained, a plurality ofX's and a plurality of X²s may be each the same.

A^(c−) represents a heteropolyoxometalate anion which is a c-valentanion and which has an oxidation-reduction potential larger than −0.3 Vrelative to the silver/silver chloride electrode. As theheteropolyoxometalate anion, examples include those exemplified above asthe heteropolyoxometalate anion as A^(c−) of the general formula (1).

A plurality of A^(c−) s may be each the same or different.

<Salt-Forming Compound Production Method>

The salt-forming compound used in the disclosed embodiments can beobtained by, for example, mixing in the solvent the organic dye of thedesired structure with the heteropolyoxometalate which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode, and heating the mixture as needed.

The organic dye of the desired structure can be synthesized withreference to the methods described in the above-described Japaneselaid-open patent applications, etc., for example.

The method for producing the compound represented by the general formula(3-1) is not particularly limited. As the production method, examplesinclude the following method: by use of a carbon-carbon forming reactionsuch as a reaction using a Grignard reagent, a coupling reaction using apalladium catalyst, an Ullmann reaction, a Friedel-Crafts reaction, anAldol reaction and a Wittig reaction, the compound that derives X¹ andX² in which Y and Z⁰ are introduced, is reacted with squaric acid in thepresence of a base.

Also, a commercially-available product may be used. As thecommercially-available product, examples include, but are not limitedto, tetraphenylporphyrin manufactured by Tokyo Chemical Industry Co.,Ltd., 5,10,15,20-tetrakis(4-sulfophenyl)porphyrin hydrate,α,β,γ,Δ-tetrakis(1-methylpyridinium-4-yl)porphyrin p-toluenesulfonate,tetrakis(4-carboxyphenyl) porphyrin,oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium(IV),5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin, 5,15-diphenylporphyrin,2,3,7,8,12,13,17,18-octaethylporphyrin,2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin,5,10,15,20-tetrakis(4-carboxymethyloxyphenyl)porphyrin,5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphyrin,5,10,15,20-tetrakis(3,5-dihydroxyphenyl)porphyrin,5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin,5,10,15,20-tetra(4-pyridyl)porphyrin,2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphyrinmanufactured by Aldrich,1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine,2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine,2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine,2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine,29H,31H-phthalocyanine, and5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine.

In the disclosed embodiments, as the color material, one kind of colormaterial can be used solely, or a combination of two or more kinds ofcolor materials can be used.

In the color material dispersion liquid of the disclosed embodiments,the content of the color material is not particularly limited. From theviewpoint of dispersibility and dispersion stability, the content of thecolor material is preferably in a range of from 5% by mass to 40% bymass of the total amount of the color material dispersion liquid, morepreferably in a range of from 10% by mass to 20% by mass thereof.

(Dispersant)

In the color material dispersion liquid of the disclosed embodiments,the color material is dispersed in the solvent and used. In thedisclosed embodiments, the dispersant is used to sufficiently dispersethe color material. The dispersant may be appropriately selected fromdispersants which are conventionally used as pigment dispersants. As thedispersant, for example, a cationic, anionic, nonionic, amphoteric,silicone-based or fluorine-based surfactant can be used. Of surfactants,a polymer surfactant (a polymer dispersant) is preferred from theviewpoint of uniform and fine dispersion.

As the polymer dispersant, examples include, but are not limited to,(co)polymers of unsaturated carboxylic acid esters such as polyacrylicacid ester; (co)polymers of unsaturated carboxylic acids such aspolyacrylic acid; (partial)amine salts, (partial)ammonium salts and(partial)alkylamine salts of (co)polymers of unsaturated carboxylicacids such as polyacrylic acid; (co)polymers of hydroxylgroup-containing unsaturated carboxylic acid esters such as hydroxylgroup-containing polyacrylic acid ester, and modified products thereof;polyurethanes; unsaturated polyamides; polysiloxanes; long-chainpolyaminoamide phosphates; polyethyleneimine derivatives (amide andsalts thereof, obtained by reaction of poly(lower alkyleneimine) andpolyester containing a free carboxyl group); polyallylamine derivatives(reaction products obtained by reacting polyallylamine and one or morecompounds selected from the following three kinds of compounds:polyester containing a free carboxyl group, polyamide and aco-condensate of ester and amide (polyester amide)).

The polymer dispersant is preferably an acidic dispersant, from thepoint of view that the color material being the salt-forming compoundcan be suitably dispersed, and excellent dispersion stability isobtained.

The acidic dispersant refers to a dispersant that the acidic groupamount is larger than the basic group amount, and a basic dispersantrefers to a dispersant that the basic group amount is larger than theacidic group amount.

As the acidic dispersant used in the disclosed embodiments, a resin thatthe acidic group amount is 80% by mole or more when the total amount ofthe acidic and basic groups is determined as 100% by mole, is preferred,and a resin which substantially contains an acidic group and which doesnot contain a basic group, is more preferred.

From the viewpoint of the dispersion stability of the color material,the acidic dispersant used in the disclosed embodiments is preferablysuch that it has an acid value and does not have an amine value.

In the case of using the acidic dispersant, the acidic dispersant isestimated to not only sufficiently disperse the color material being thesalt-forming compound but also have the function of allowing the colormaterial being the salt-forming compound to be stably present in thestate of ion pair.

The acid value of the acidic dispersant used in the disclosedembodiments is preferably 30 mgKOH/g or more, more preferably 60 mgKOH/gor more, and still more preferably 90 mgKOH/g or more.

The amine value of the acidic dispersant used in the present inventionis preferably 0 mgKOH/g.

The acid value represents the mass (mg) potassium hydroxide needed toneutralize the acidic component contained in per gram of the solidcontent of the dispersant, and it is a value measured by the methoddescribed in JIS K 0070.

The amine value represents the mass (mg) of potassium hydroxide, whichis an equivalent to the amount of hydrochloric acid needed to neutralizeone gram of the solid content of the dispersant, and it is a valuemeasured by the method described in JIS K 7237.

As the acidic group of the acidic dispersant used in the disclosedembodiments, examples include, but are not limited to, a carboxy group,a phosphoric acid group and a salt thereof, and a sulfonic acid groupand a salt thereof.

As the acidic dispersant, examples include, but are not limited to, ablock or graft copolymer containing an acidic group; a salt of a blockcopolymer containing an acidic group with an organic cation such as analkylammonium salt; a hydroxyl group-containing carboxylic acid ester; afatty acid salt such as a salt of a high-molecular-weight polycarboxylicacid; a polyether ester-type anionic surfactant; a naphthalene sulfonicacid formalin condensate salt; a phosphoric acid ester such as apolyoxyethylene alkyl phosphoric acid ester and a salt thereof; alkylsulfate ester salt; a polyoxyethylene alkyl ether sulfate ester salt;and a sulfonic acid salt such as an alkyl benzene sulfonic acid salt.

As commercially-available products of the acidic dispersant, examplesinclude, but are not limited to, DISPERBYKR-103, DISPERBYKR-110,DISPERBYK-118, AJISPER PN411 and AJISPER PA111.

Of acidic dispersants, from the viewpoint of the dispersibility anddispersion stability of the color material, the dispersant is morepreferably a polymer containing one or more selected from theconstitutional unit represented by the following general formula (I) andthe constitutional unit represented by the following general formula(I′):

where L¹ is a direct bond or a divalent linking group; R³¹ is a hydrogenatom or a methyl group; R³² is a hydroxyl group, a hydrocarbon group ora monovalent group represented by —[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵,—[(CH₂)_(y1)—O]_(z1)—R³⁵ or —O—R³⁶; R³⁶ is a hydrocarbon group or amonovalent group represented by—[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵,—[(CH₂)_(y1)—O]_(z1)—R³⁵, —C(R³⁷)(R³⁸)—C(R³⁹) (R⁴⁰)—OH or —CH₂—C(R⁴¹) (R⁴²)—CH₂—OH;

R³³ and R³⁴ are each independently a hydrogen atom or a methyl group;R³⁵ is a hydrogen atom, a hydrocarbon group or a monovalent grouprepresented by —CHO, —CH₂CHO, —CO—CH═CH₂, —CO—C(CH₃)═CH₂ or —CH₂COOR⁴³;R⁴³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹ and R⁴² are each independently a hydrogen atom,a hydrocarbon group or a hydrocarbon group containing one or moreselected from an ether bond and an ester bond; R³⁷ and R³⁹ may be boundto each other to form a ring structure; when the ring structure isformed, the ring structure may further contain a substituent R⁴⁴, andR⁴⁴ is a hydrocarbon group or a hydrocarbon group containing one or moreselected from an ether bond and an ester bond; the hydrocarbon group maycontain a substituent; and in the general formula (I′), X⁺ represents anorganic cation, and x1, y1 and z1 represent an integer of from 1 to 18,an integer of from 1 to 5, and an integer of from 1 to 18, respectively.

In the general formulae (I) and (I′), L¹ is a direct bond or a divalentlinking group. When L¹ is a direct bond, it means that a phosphorus atomis directly bound to the carbon atom of the main chain, not through thelinking group.

The divalent linking group as L¹ is not particularly limited, as long asthe carbon atom of the main chain and the phosphorus atom can be linkedto each other. As the divalent linking group as L¹, examples include,but are not limited to, a linear, branched or cyclic alkylene group, alinear, branched or cyclic alkylene group containing a hydroxyl group,an arylene group, a —CONH— group, a —COO— group, a —NHCOO— group, anether group (a —O— group), a thioether group (a —S— group) andcombinations thereof. In the present invention, the binding direction ofthe divalent linking group may be any direction. That is, when —CONH— iscontained in the divalent linking group, —CO may be on the carbon atomside of the main chain, and —NH may be on the phosphorus atom side ofthe side chain. To the contrary, —NH may be on the carbon chain side ofthe main chain, and —CO may be on the phosphorus atom side of the sidechain.

From the viewpoint of dispersibility, L¹ of the general formulae (I) and(I′) is preferably a divalent linking group containing a —CONH— group ora —COO— group, and more preferably a —CONH-L¹′ group or a —COO-L¹′group. L¹′ is an alkylene group having 1 to 8 carbon atoms andoptionally containing a hydroxyl group, —[CH(R^(a))—CH(R^(b))—O]_(x)—,—[(CH₂)_(y)—O]_(z)—(CH₂)_(y)—O—, or —[CH(R^(c))]_(w)—O—, and R^(a),R^(b) and R^(c) are preferably each independently a hydrogen atom, amethyl group or a hydroxyl group.

The alkylene group having 1 to 8 carbon atoms as L¹′ may be any oflinear, branched or cyclic. As the alkylene group having 1 to 8 carbonatoms, examples include, but are not limited to, a methylene group, anethylene group, a trimethylene group, a propylene group, various kindsof butylene groups, various kinds of pentylene groups, various kinds ofhexylene groups, and various kinds of octylene groups. Part of thehydrogen may be substituted by a hydroxyl group.

Also, x is an integer of from 1 to 18, preferably an integer of from 1to 4, and more preferably an integer of from 1 to 2; y is an integer offrom 1 to 5, preferably an integer of from 1 to 4, and more preferably 2or 3; z is an integer of from 1 to 18, preferably an integer of from 1to 4, and more preferably an integer of from 1 to 2; and w is an integerof from 1 to 18, and preferably an integer of from 1 to 4.

Preferred examples of L¹ of the general formulae (I) and (I′) include,but are not limited to, —COO—CH₂CH(OH)CH₂—O—,—COO—CH₂CH₂—O—CH₂CH(OH)CH₂—O—, and —COO—CH₂C(CH₂CH₃)(CH₂OH)CH₂—O—.

As the hydrocarbon group as R³², examples include, but are not limitedto, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having2 to 18 carbon atoms, an aralkyl group and an aryl group.

The alkyl group having 1 to 18 carbon atoms may be any of linear,branched, cyclic. As the alkyl group, examples include, but are notlimited to, a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, a cyclopentyl group, a cyclohexylgroup, a bornyl group, an isobornyl group, a dicyclopentanyl group, anadamantyl group and a lower alkyl group substituted adamantyl group.

The alkenyl group having 2 to 18 carbon atoms may be any of linear,branched, cyclic. As such an alkenyl group, examples include, but arenot limited to, a vinyl group, an allyl group and a propenyl group. Theposition of the double bond of the alkenyl group is not particularlylimited. From the viewpoint of the reactivity of the obtained polymer,the alkenyl group preferably contains the double bond at the terminal.

As the aryl group, examples include, but are not limited to, a phenylgroup, a biphenyl group, a naphthyl group, a tolyl group and a xylylgroup. The aryl group may further contain a substituent. The aryl grouppreferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbonatoms.

As the aralkyl group, examples include, but are not limited to, a benzylgroup, a phenethyl group, a naphthylmethyl group and a biphenylmethylgroup. The aralkyl group may further contain a substituent. The aralkylgroup preferably has 7 to 20 carbon atoms, and more preferably 7 to 14carbon atoms.

The alkyl group and the alkenyl group may contain a substituent. As thesubstituent, examples include, but are not limited to, a halogen atomsuch as F, Cl, Br, and a nitro group.

As the substituent of the aromatic ring such as the aryl group and thearalkyl group, examples include, but are not limited to, a linear,branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, anitro group and a halogen atom.

The preferred carbon atom number does not include the number of thecarbon atoms of the substituent.

For R³², x1, y1 and z1 are the same as the above-described x, y and z,respectively.

As the hydrocarbon group as R³⁵ to R⁴², examples include thoseexemplified above as the hydrocarbon group as R³².

The hydrocarbon group containing one or more selected from an ether bondand an ester bond as R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹ and R⁴² is a grouprepresented by —R′—O—R″, —R′—(C═O)—O—R″ or —R′—O—(C═O)—R″ (where R′ andR″ are each a hydrocarbon group or such a group that a hydrocarbon groupis bound by at least one of an ether bond and an ester bond). In onegroup, two or more ether bonds and ester bonds may be present. When thehydrocarbon group is monovalent, as the hydrocarbon group, examplesinclude an alkyl group, an alkenyl group, an aralkyl group and an arylgroup. When the hydrocarbon group is divalent, as the hydrocarbon group,examples include an alkylene group, an alkenylene group, an arylenegroup and combinations thereof.

When R³⁷ and R³⁹ are bound to form a ring structure, the number ofcarbon atoms forming the ring structure is preferably from 5 to 8, andmore preferably 6 (that is, 6-membered). The formed ring structure ispreferably a cyclohexane ring.

As the hydrocarbon group or the hydrocarbon group containing one or moreselected from an ether bond and an ester bond as the substituent R⁴⁴,examples include those exemplified above as the hydrocarbon groups asR³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹ and R⁴².

From the viewpoint of excellent dispersibility and dispersion stabilityof dispersed particles, R³² is preferably a hydroxyl group, ahydrocarbon group, a monovalent group represented by—[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵, —[(CH₂)_(y1)—O]_(z1)—R³⁵ or —O—R³⁶, morepreferably a hydroxyl group, a methyl group, an ethyl group, a vinylgroup, an aryl or aralkyl group optionally containing a substituent, avinyl group, an allyl group, a monovalent group represented by—[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵, —[(CH₂)_(y1)—O]_(z1)—R³⁵ or —O—R³⁶ (whereR³³ and R³⁴ are each independently a hydrogen atom or a methyl group,and R³⁵ is —CO—CH═CH₂ or —CO—C(CH₃)═CH₂). R³² is still more preferablyan aryl group optionally containing a substituent, a vinyl group, amethyl group and a hydroxyl group.

From the viewpoint of increasing alkali resistance, R³² is preferably ahydrocarbon group, a monovalent group represented by—[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵ or —[(CH₂)_(y1)—O]—R³⁵. When having thestructure that a carbon atom is directly bound to a phosphorus atom, dueto hydrolysis resistance, it is estimated that a resin layer withexcellent alkali resistance can be produced. From the viewpoint ofexcellent alkali resistance and excellent dispersibility and dispersionstability of dispersed particles, R³² is preferably a methyl group, anethyl group, an aryl or aralkyl group optionally containing asubstituent, a vinyl group, an allyl group, a monovalent grouprepresented by —[CH(R³³)—CH(R³⁴)—O]_(x1)—R³⁵ or —[(CH₂)_(y1)—O]_(z1)—R³⁵(where R³³ and R³⁴ are each independently a hydrogen atom or a methylgroup, and R³⁵ is —CO—CH═CH₂ or —CO—C(CH₃)═CH₂). From the viewpoint ofdispersibility, R³² is more preferably an aryl group optionallycontaining a substituent.

Also, X⁺ of the general formula (I′) represents an organic cation. Theorganic cation refers to a cation that the cation moiety contains acarbon atom. As the organic cation, examples include, but are notlimited to, an ammonium cation such as an imidazolium cation, apyridinium cation, an amidinium cation, a piperidinium cation, apyrrolidinium cation, a tetraalkylammonium cation and a trialkylammoniumcation, a sulfonium cation such as a trialkylsulfonium cation, and aphosphonium cation such as a tetraalkylphosphonium cation. From theviewpoint of dispersibility and alkaline developability, the organiccation is preferably a protonated, nitrogen-containing organic cation.

The organic cation preferably has an ethylenically unsaturated doublebond, since curability can be provided.

From the point of view that excellent color material dispersibility andstorage stability can be obtained and the film excellent in heatresistance and solvent resistance can be formed, the polymer containingone or more selected from the constitutional unit represented by thegeneral formula (I) and the constitutional unit represented by thegeneral formula (I′), as the (B) dispersant, is preferably such apolymer that is a reaction product of an acidic phosphorus compound anda polymer containing at least one of an epoxy group and a cyclic ethergroup in the side chain, and at least part of the acidic phosphoruscompound groups may form a salt.

From the viewpoint of dispersibility, the polymer containing one or moreselected from the constitutional unit represented by the general formula(I) and the constitutional unit represented by the general formula (I′),preferably further has a solvent-affinity moiety. From the point of viewthat excellent color material dispersibility and storage stability canbe obtained and the film excellent in heat resistance and solventresistance can be formed, such a dispersant is preferably a graftcopolymer containing one or more selected from the constitutional unitrepresented by the general formula (I) and the constitutional unitrepresented by the general formula (I′) and a constitutional unitrepresented by the following general formula (II), or a block copolymercontaining the constitutional unit represented by the general formula(I) and the constitutional unit represented by the general formula (I′)and a constitutional unit represented by the following general formula(III):

in the general formula (II), L² represents a direct bond or a divalentlinking group; R⁵¹ represents a hydrogen atom or a methyl group; andPolymer represents a polymer chain containing a constitutional unitrepresented by the following general formula (IV);

in the general formula (III), R⁵² is a hydrogen atom or a methyl group;R⁵³ is a hydrocarbon group, a monovalent group represented by—[CH(R⁵⁴)—CH(R⁵⁵)—O]_(x2)—R⁵⁶, —[(CH₂)_(y2)—O]_(z2)—R⁵⁶,—[CO—(CH₂)_(y2)—O]_(z2)—R⁵⁶, —CO—O—R^(56′) or —O—CO—R^(56″); R⁵⁴ and R⁵⁵are each independently a hydrogen atom or a methyl group; R⁵⁶ is ahydrogen atom, a hydrocarbon group, a monovalent group represented by—CHO, —CH₂CHO or —CH₂COOR⁵⁷; R^(56′) is a hydrocarbon group, amonovalent group represented by —[CH(R⁵⁴)—CH(R⁵⁵)—O]_(x2′)—R⁵⁶,—[(CH₂)_(y2′)—O]_(z2′)—R⁵⁶, —[CO—(CH₂)_(y2′)—O]_(z2′)—R⁵⁶; R⁵⁶″ is analkyl group having 1 to 18 carbon atoms; R⁵⁷ is a hydrogen atom or analkyl group having 1 to 5 carbon atoms; the hydrocarbon group maycontain a substituent; x2 and x2′ are each an integer of from 1 to 18;y2 and y2′ are each an integer of from 1 to 5; and z2 and z2′ are eachan integer of from 1 to 18;

in the general formula (IV), R⁶¹ is a hydrogen atom or a methyl group;R⁶² is a hydrocarbon group, a monovalent group represented by—[CH(R⁶³)—CH(R⁶⁴)—O]_(x3)—R⁶⁵, —[(CH₂)_(y3)—O]_(z3)—R⁶⁵,—[CO—(CH₂)_(y3)—O]_(z3)—R⁶⁵, —CO—O—R⁶⁶ or —O—CO—R⁶⁷; R⁶³ and R⁶⁴ areeach independently a hydrogen atom or a methyl group; R⁶⁵ is a hydrogenatom, a hydrocarbon group, a monovalent group represented by —CHO,—CH₂CHO or —CH₂COOR⁶⁸; R⁶⁶ is a hydrocarbon group, a monovalent grouprepresented by —[CH(R⁶³)—CH(R⁶⁴)—O]_(x4)—R⁶⁵,—[(CH₂)_(y4)—O]_(z4)—R⁶⁵,—[CO— (CH₂)_(y4)—O]_(z4)—R⁶⁵; R⁶⁷ is an alkylgroup having 1 to 18 carbon atoms; R⁶⁸ is a hydrogen atom or an alkylgroup having 1 to 5 carbon atoms; the hydrocarbon group may contain asubstituent;

n represents an integer of from 5 to 200; x3 and x4 are each an integerof from 1 to 18; y3 and y4 are each an integer of from 1 to 5; and z3and z4 are each an integer of from 1 to 18.

Preferred examples of the graft copolymer containing one or moreselected from the constitutional unit represented by the general formula(I) and the constitutional unit represented by the general formula (I′)and the constitutional unit represented by the general formula (II) orthe block copolymer containing one or more selected from theconstitutional unit represented by the general formula (I) and theconstitutional unit represented by the general formula (I′) and theconstitutional unit represented by the general formula (III), includegraft and block copolymers described in JP-A No. 2017-002191, etc.

In the disclosed embodiments, as the dispersant, one kind of dispersantmay be used solely, or a combination of two or more kinds of dispersantsmay be used. The content of the dispersant is appropriately determineddepending on the type of the color material used, etc. In the colormaterial dispersion liquid of the disclosed embodiments, with respect to100 parts by mass of the color material, the dispersant is generally ina range of from 5 parts by mass to 200 parts by mass, preferably in arange of from 10 parts by mass to 100 parts by mass, and more preferablyin a range of from 20 parts by mass to 80 parts by mass. When thecontent is in the range, the color material can be uniformly dispersed.Also, the ratio of the binder component contained in the compositiondescribed below, is not relatively low, the film with sufficienthardness can be formed.

In the color material dispersion liquid of the disclosed embodiments,with respect to the total amount of the dispersion liquid, the contentof the dispersant is generally in a range of from 1% by mass to 50% bymass, and preferably from 1% by mass to 20% by mass, from the viewpointof dispersibility and dispersion stability.

(Solvent)

In the color material dispersion liquid of the disclosed embodiments,the color material is used in the state of particles (aggregates) bydispersing the color material in the solvent. Since the color materialis the above-specified salt-forming compound of the organic dye with theheteropolyoxometalate, it is hardly soluble in organic solvents. Thecolor material being the salt-forming compound used in the disclosedembodiments is used by dispersing the color material in the solventwhile keeping its aggregation state, thereby obtaining excellent lightresistance. The solvent used in the disclosed embodiments is preferablya solvent in which the color material being the salt-forming compound issubstantially insoluble or is hardly soluble and which has a solubilityof 0.1 (mg/10 g solvent) or less at 23° C. The solvent is preferably asolvent in which the color material has a solubility of 0.01 (mg/10 gsolvent) or less at 23° C., and more preferably a solvent in which thecolor material is substantially insoluble.

In the disclosed embodiments, the solvent in which the color materialbeing the salt-forming compound has a solubility of 0.1 (mg/10 gsolvent) or less at 23° C., can be simply determined by the followingevaluation method.

First, 10 g the solvent, which is an object of evaluation, is put in a20 mL sample tube bottle. In addition, 0.1 g of the color material isput in the sample tube bottle. The bottle is capped and shaken well for20 seconds. Then, the bottle is left to stand for 10 minutes in a waterbath at 23° C. Next, 5 g of the resulting supernatant is filtered forthe removal of insoluble matters. The filtered supernatant is diluted1000 times to obtain a solution, and the absorption spectrum of thesolution is measured by using a 1 cm cell in a UV-VIS-NIRspectrophotometer (e.g., UV-3100PC manufactured by Shimadzu Corporation)to obtain an absorbance at the maximum absorption wavelength. When theabsorbance at the maximum absorption wavelength is less than 2, thesolvent can be evaluated as a solvent in which the color material has asolubility of 0.1 (mg/10 g solvent) or less at 23° C. (i.e., ahardly-soluble solvent).

In the above-described evaluation method, the absorption spectrum ismeasured in the same manner as above, without diluting the obtainedsupernatant, and the absorbance at the maximum absorbance wavelength isobtained. When the absorbance at the maximum absorption wavelength isless than 2, the solvent can be evaluated as a solvent in which thecolor material being the salt-forming compound, is substantiallyinsoluble.

The solvent in which the color material has a solubility of 0.1 (mg/10 gsolvent) or less at 23° C., is not particularly limited, as long as itis a solvent in which the color material being the salt-formingcompound, is substantially insoluble, or as long as it is ahardly-soluble solvent. The solvent can be appropriately selected fromsolvents which are unreactive to the components of the color materialdispersion liquid and in which the components are soluble ordispersible.

In the color material dispersion liquid of the disclosed embodiments,from the viewpoint of dispersion stability, an ester solvent ispreferably used.

As the ester solvent, examples include, but are not limited to, ethylacetate, butyl acetate, methyl methoxypropionate, ethylethoxypropionate, ethyl lactate, methoxyethyl acetate, propylene glycolmonomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate,3-methoxybutyl acetate, methoxy butyl acetate, ethoxy ethyl acetate andethyl cellosolve acetate.

These solvents may be used solely or in combination of two or morekinds.

The color material dispersion liquid of the disclosed embodiments isprepared by using the above-described solvent in an amount of generallyfrom 50% by mass to 95% by mass, preferably from 60% by mass to 85% bymass, with respect to the total amount of the color material dispersionliquid containing the solvent. When the solvent amount is too small, theviscosity increases, and the dispersibility is likely to decrease. Whenthe solvent amount is too large, the color material concentrationdecreases and, depending on the intended application, there is apossibility that the effect of absorbing light of the specificwavelength is not insufficient.

(Other components)

As needed, the color material dispersion liquid of the disclosedembodiments may further contain other color material, a dispersionassisting resin and other components.

Other color material is added as needed, for the purpose of color tonecontrol. It can be selected from conventionally-known color materialssuch as pigments and dyes, according to the purpose, and such colormaterials can be used alone or in combination of two or more kinds. Thecontent of the other color material is not particularly limited, as longas the effect of the disclosed embodiments are not impaired. It may bethe same as the case where it is used in the composition describedbelow.

As the dispersion assisting resin, examples include, but are not limitedto, an alkali soluble resin. The particles of the color material becomeless likely to contact with each other due to steric hindrance by thealkali soluble resin, resulting in stabilization of particle dispersion,and the particle dispersion stabilization effect may be effective inreducing the dispersant.

As the other components, examples include, but are not limited to, asurfactant, which is used to increase wettability, a silane couplingagent, which is used to increase adhesion properties, a defoaming agent,a cissing inhibitor, an antioxidant, an aggregation inhibitor and anultraviolet absorber.

<Method for Producing the Color Material Dispersion Liquid>

The color material dispersion liquid of the disclosed embodiments can beprepared by the following method: the dispersant is mixed with thesolvent and stirred to produce a dispersant solution; the dispersantsolution is mixed with the color material of the disclosed embodimentsand, as needed, other compound; and the mixture is dispersed with adisperser, thereby preparing the color material dispersion liquid. Also,the color material dispersion liquid of the disclosed embodiments may beprepared by mixing the color material and the dispersant with thesolvent, and dispersing the mixture by use of a known disperser.

As the disperser used for the dispersion treatment, examples include,but are not limited to, a roller mill such as a two-roller mill and athree-roller mill; a ball mill such as a vibrating ball mill; a paintconditioner; and a bead mill such as a continuous disk type bead milland a continuous annular type bead mill. In the case of using a beadmill, a preferred dispersion condition is such that the diameter of thebeads used is preferably from 0.03 mm to 2.00 mm, and more preferablyfrom 0.10 mm to 1.0 mm.

In particular, a preparatory dispersion is carried out with 2 mmzirconia beads, which is a relatively large bead diameter, and then amain dispersion is further carried out with 0.1 mm zirconia beads, whichis a relatively small bead diameter. It is preferable to carry outfiltration with a 0.1 to 0.5 μm membrane filter after the dispersiontreatment.

In the disclosed embodiments, the dispersion time for dispersion using aknown dispersing device, is appropriately controlled and is notparticularly limited. For example, the dispersion time is preferablyfrom 5 hours 40 hours, from the viewpoint of forming the color materialinto fine particles and achieving high absorption properties withrespect to the light in the unnecessary wavelength range.

The color material dispersion liquid excellent in the dispersibility ofthe color material particles, is obtained in this manner.

In the color material dispersion liquid, the average dispersed particlediameter of the color material used in the disclosed embodiments, may beappropriately determined depending on the intended application and isnot particularly limited. From the viewpoint of obtaining excellentlight resistance, the average dispersed particle diameter is preferablyin a range of from 10 nm to 150 nm, and more preferably in a range offrom 20 nm to 125 nm. By setting the average dispersed particle diameterof the color material within the range, a surface coated with the colormaterial dispersion liquid of the disclosed embodiments exhibits uniformand excellent absorption performance with respect to the light in theunnecessary wavelength range.

The average dispersed particle diameter of the color material in thecolor material dispersion liquid is the dispersed particle diameter ofthe color material particles dispersed in a dispersion medium thatcontains at least a solvent, and it is measured with a laser scatteringparticle size distribution analyzer. The average dispersed particlediameter can be measured as follows with a laser scattering particlesize distribution analyzer: the color material dispersion liquid isappropriately diluted with the solvent used for the color materialdispersion liquid to a concentration that is measurable with a laserscattering particle size distribution analyzer (e.g., 1,000-fold) andthen measured with a laser scattering particle size distributionanalyzer (e.g., NANOTRAC PARTICLE SIZE ANALYZER UPA-EX150 manufacturedby Nikkiso Co., Ltd.) by a dynamic light scattering method at 23° C.This average dispersed particle diameter is a volume average particlediameter.

The color material dispersion liquid can be used as a preliminarilyprepared product for preparing the below-described composition. That is,the color material dispersion liquid is such a color material dispersionliquid, that it is preliminarily prepared at a stage prior to preparingthe below-described composition and the ratio of “the mass of the colormaterial in the composition”/“the mass of the solid content other thanthe color material in the composition” is high. In particular, thisratio (“the mass of the color material in the composition”/“the mass ofthe solid content other than the color material in the composition”ratio) is generally 1.0 or more. By mixing the color material dispersionliquid with at least a binder component, a composition with excellentdispersibility can be prepared.

B. Composition

The composition of the disclosed embodiments contains a color material,which is a salt-forming compound of an organic dye with aheteropolyoxometalate, and a binder component,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

In the composition of the disclosed embodiments, by using the colormaterial which is the salt-forming compound of the predetermined organicdye with the heteropolyoxometalate having an oxidation-reductionpotential larger than −0.3 V relative to the silver/silver chlorideelectrode (hereinafter, the color material may be referred to as thespecific color material used in the disclosed embodiments) incombination with the binder component, a film with excellent lightresistance can be formed while selectively and effectively reducing thelight in the unnecessary wavelength range.

The composition of the disclosed embodiments contains at least thespecific color material used in the disclosed embodiments and the bindercomponent. As needed, the composition may further contain othercomponents.

Also in the composition of the disclosed embodiments, the color materialdispersion liquid may be used in combination with the binder component.In this case, the composition of the disclosed embodiments contains thespecific color material used in the disclosed embodiments, the bindercomponent, the dispersant and the solvent.

Hereinafter, the components of the composition of the disclosedembodiments will be described in detail. As the components that can becontained in the color material dispersion liquid of the disclosedembodiments, those described above in “A. Color material dispersionliquid” may be used. Accordingly, the components will not be describedhere. However, the solvent is not limited to the above-describedpreferred solvent, and a solvent in which the solubility of the bindercomponent and other components added as needed is high, may beappropriately selected and used as the solvent.

(Binder Component)

To provide film-forming properties and surface adhesion properties, thecomposition of the disclosed embodiments contains a binder component.

The binder component preferably contains at least a resin. The resin maybe any of a pressure-sensitive adhesive, a thermoplastic resin, athermosetting resin or a photocurable resin. The resin is not limited toa high-molecular-weight compound or a polymer, and the resin may be alow-molecular-weight compound or a monomer.

The binder component preferably has optical transparency. When only thebinder component is used to form a film having the same film thicknessof the film of the disclosed embodiments, the transmittance in thevisible light range is preferably 80% or more, and more preferably 84%or more. The transmittance can be measured by JIS K7361-1 (Determinationof the total luminous transmittance of plastics-transparent materials).

As the pressure-sensitive adhesive, examples include, but are notlimited to, an acrylic pressure-sensitive adhesive, a siliconepressure-sensitive adhesive, a urethane pressure-sensitive adhesive, apolyvinyl butyral pressure-sensitive adhesive, an ethylene-vinyl acetatepressure-sensitive adhesive, polyvinyl ether, saturated amorphouspolyester and melamine resin.

As the thermoplastic resin, for example, the following are preferred:epoxy resin; acrylic resin such as polymethyl methacrylate andpolyacrylic acid amide; polystyrene resin; cellulose resin such asnitrocellulose and ethylcellulose; polyester resin; thermoplasticurethane resin; modified olefin resin such as chlorinated polyethyleneand chlorinated polypropylene; vinyl resin such as vinyl acetate resin,vinyl chloride-vinyl acetate copolymer and butyral resin; and amorphouspolyolefin having a norbornene structure. The glass transitiontemperature of the resin is preferably in a range of from 90° C. to 180°C., and particularly preferably in a range of from 120° C. to 180° C.

From the viewpoint of providing sufficient hardness to coating films,the composition preferably contains a curable binder component thatcontains a thermosetting resin or a photocurable resin. The curablebinder component is not particularly limited, and a conventionally-knowncurable binder component can be appropriately used.

As the curable binder component, for example, one containing aphotocurable binder component that contains a photocurable resin, whichis polymerizable and curable by visible light, ultraviolet, electronbeam radiation, etc., or one containing a thermosetting binder componentthat contains a thermosetting resin, which is polymerizable and curableby heating, can be used.

As the thermosetting binder, a combination of a curing agent and acompound containing two or more thermosetting functional groups permolecule, is generally used. In addition, a catalyst that can promote athermosetting reaction can be added. As the thermosetting functionalgroups, examples include, but are not limited to, an epoxy group, anoxetanyl group, an isocyanate group and an ethylenically unsaturatedbond. As the thermosetting functional groups, epoxy groups arepreferably used. As the thermosetting binder component, examplesinclude, but are not limited to, those mentioned in InternationalPublication No. WO2012/144521.

As the photocurable binder, a combination of a photoinitiator and acompound containing one or more photocurable functional groups permolecule, is generally used. The compound and photoinitiator can beappropriately selected from conventionally-known compounds andphotoinitiators and used. As the photocurable functional group, examplesinclude, but are not limited to, radically polymerizable, ethylenicallyunsaturated bond-containing group, a cationically polymerizable epoxygroup and an oxetanyl group. As the photocurable functional group, anethylenically unsaturated bond-containing group is preferably used, suchas a vinyl group and a (meth)acryloyl group.

From the viewpoint of increasing hardness, the photocurable compoundpreferably contains three or more photocurable functional groups permolecule.

As the radically polymerizable compound, from the viewpoint of highreactivity, a compound containing a (meth)acryloyl group is preferred.Also, a compound containing 2 to 6 (meth)acryloyl groups per molecule,which is referred to as polyfunctional (meth)acrylate monomer, and anoligomer containing several (meth)acryloyl groups per molecule andhaving several hundreds to several thousands of molecular weight, whichis referred to as urethane (meth)acrylate, polyester (meth)acrylate,epoxy (meth)acrylate, are preferably used.

When the film has a pattern and a photolithography process is used inthe formation of the film, a photosensitive binder component withalkaline developability is preferably used.

As the photosensitive binder component, examples include, but are notlimited to, a positive photosensitive binder component and a negativephotosensitive binder component. As the positive photosensitive bindercomponent, examples include, but are not limited to, a system containingan alkali soluble resin and an o-quinonediazide group-containingcompound, which is a photosensitivity-imparting component. As the alkalisoluble resin, examples include, but are not limited to, a polyimideprecursor.

As the negative photosensitive binder component, a system containing atleast an alkali soluble resin, a polyfunctional monomer and aphotoinitiator, is suitably used. As the alkali soluble resin,polyfunctional monomer and photoinitiator, examples include, but are notlimited to, those described in International Publication No.WO2012/144521.

(Optionally Added Components)

As needed, the composition of the disclosed embodiments may containother color material or various kinds of additives, to the extent thatdoes not impair the object of the disclosed embodiments.

As the additives, examples include, but are not limited to, apolymerization inhibitor, a chain transfer agent, a leveling agent, aplasticizer, a surfactant, a defoaming agent, a silane coupling agent,an ultraviolet absorber, an adhesion enhancing agent, an antistaticagent and a filler.

As the surfactant and the plasticizer, examples include, but are notlimited to, those mentioned in International Publication No.WO2012/144521.

(The Content of Each Component in the Composition)

The total content of the specific color material used in the disclosedembodiments and the other color material added as needed, is preferablyfrom 0.1% by mass to 20% by mass, and more preferably from 0.2% by massto 10% by mass, with respect to the total solid content of thecomposition. When the amount of the color material is too small, it maybe difficult to obtain desired absorption properties with respect to thelight in the unnecessary wavelength range. When the amounts of the colormaterial, etc., is too large, the properties of a coating film formed byapplying the composition to a substrate and curing the appliedcomposition, such as adhesion to the substrate, surface roughening ofthe cured film and the hardness of the coating film, may beinsufficient. In the disclosed embodiments, “solid content” refers toall of the above-described components other than the solvent, and italso includes a polyfunctional monomer that is in a liquid form at 25°C.

In the case of using the dispersant, the content of the dispersant maybe appropriately controlled in a range where the color material can behomogeneously dispersed. For example, the dispersant content ispreferably from 10 parts by mass to 150 parts by mass, with respect to100 parts by mass of the color material. Also, the content is morepreferably from 15 parts by mass to 45 parts by mass, and still morepreferably from 15 parts by mass to 40 parts by mass, with respect to100 parts by mass of the color material. With respect to the total solidcontent of the composition, the content of the dispersant is preferablyin a range of from 0.01% by mass to 30% by mass, and particularlypreferably in a range of from 0.03% by mass to 10% by mass. When thecontent of the dispersant is less than 0.01% by mass with respect to thetotal solid content of the composition, the effect produced by using thedispersant may be insufficient. When the content of the dispersant ismore than 30% by mass, insufficient hardness and developability may beobtained.

For the amount of the binder component, the total content is preferablyfrom 24% by mass to 94% by mass, more preferably from 40% by mass to 90%by mass, with respect to the total solid content of the composition.

In the case of using the solvent, the content can be appropriatelycontrolled depending on the dispersibility of the color material, thecoatability of the composition, etc. In general, with respect to thetotal amount of the composition containing the solvent, the solvent ispreferably in a range of from 65% by mass to 95% by mass, and morepreferably in a range of from 75% by mass to 88% by mass.

(Production of Composition)

The method for producing the composition is not particularly limited.

In the case of using a pressure-sensitive adhesive or thermoplasticresin as the binder component, the specific color material used in thedisclosed embodiments, may be added to the pressure-sensitive adhesiveor thermoplastic resin, and they are mixed or kneaded together and used.

Also, there is the following method: the binder component and variouskinds of additional components used as needed, are added to the solvent;they are mixed together; the color material used in the disclosedembodiments is added to the mixture; and they are mixed together.

In the case of preparing the composition using the color materialdispersion liquid of the disclosed embodiments, there may be mentionedthe following methods, for example: a method of adding the colormaterial dispersion liquid of the disclosed embodiments, the bindercomponent and various kinds of additional components used as needed tothe solvent at the same time and mixing them, and a method of adding thebinder component and various kinds of additional components used asneeded to the solvent, mixing them, adding the color material dispersionliquid of the disclosed embodiments thereto and then mixing them.

C. Film

The film of the disclosed embodiments is a film comprising thecomposition of the disclosed embodiments or a cured product thereof.

The film of the disclosed embodiments may have a pattern, or it may be afilm having no pattern (i.e., a flat film). Also, the film of thedisclosed embodiments may be used in the state of being laminated on asupport, or the film of the disclosed embodiments may be removed fromthe substrate and used.

The film thickness of the film of the disclosed embodiments may beappropriately controlled depending on the purpose. The film thickness ispreferably 50 μm or less, more preferably 25 μm or less, and still morepreferably 10 μm or less. The lower limit of the film thickness ispreferably 0.1 μm or more, more preferably 0.2 μm or more, and stillmore preferably 0.3 μm or more.

Since the film of the disclosed embodiments contains the specific colormaterial used in the present invention, the film has high lightresistance, and the film is less likely to cause a change in spectralcharacteristics, which is attributed to the deterioration of the colormaterial, even after a long-term use. In particular, before and afterthe following light resistance test is carried out, the retention rateof the transmittance value of the maximum absorption wavelength of thedye, that is the minimum transmission wavelength of the transmissionspectrum, is preferably 70% or more, and more preferably 80% or more.

Also, before and after the following light resistance test is carriedout, the thus-obtained color difference (ΔEab) is preferably 25 or less,and more preferably 20 or less.

(Light Resistance Test)

A film in which the concentration of the specific color material used inthe disclosed embodiments is 8% by mass and which have a film thicknessof 3 μm, is produced. Under the atmospheric pressure, the film isirradiated with a xenon lamp (SUNTEST XLS+(a 1.7 kW air-cooled xenonlamp) manufactured by ATLAS) at a wavelength of from 300 nm to 400 nmand an irradiance of 58 W/m² for 60 hours (equivalent to 11000 kJ/m²).The retention rate of the transmittance value of the minimumtransmission wavelength of the transmission spectrum before and afterthe irradiation, is calculated by the following formula (1). The colordifference (ΔEab) before and after the irradiation is calculated by thefollowing formula (2). The color coordinates L, a, b of the film beforebeing subjected to the irradiation, are determined as (L₁, a₁, b₁), andthe color coordinates L, a, b of the film after the irradiation aredetermined as (L₂, a₂, b₂).The retention rate=(100−The transmittance (%) of the minimumtransmission wavelength after the test)/(100−The transmittance (%) ofthe minimum transmission wavelength before the test)×100  Formula (1):ΔEab={(L ₂ −L ₁)²+(a ₂ −a ₁)²+(b ₂ −b _(l))²}^(1/2)  Formula (2):

As the method for producing the film of the disclosed embodiments, forexample, there may be mentioned a method comprising the step of forminga composition layer on a support by use of the composition of thedisclosed embodiments and, as needed, the step of curing the compositionlayer.

The support is not particularly limited. The support may be a supportcomposed of a material such as glass, silicon, polycarbonate, polyester,polyacrylic, aromatic polyamide, polyamideimide, polyimide, cycloolefinpolymer and cellulose acylate, or it may be a different optical memberused in display devices.

The method for applying the composition to the support may beappropriately selected from known methods and used. As the knownmethods, examples include, but are not limited to, composition applyingmethods such as a gravure coating method, a reverse coating method, aknife coating method, a dip coating method, a spray coating method, anair knife coating method, a spin coating method, a roll coating method,a printing method, a dipping method, a curtain coating method, a diecoating method, a casting method, a bar coating method, an extrusioncoating method and an E-type applying method; various kinds of printingmethods such as an ejection type printing method (e.g., inkjet printingand nozzle-jet printing), a flexographic printing method, a screenprinting method, a gravure printing method, a reverse offset printingmethod and a metal mask printing method; transfer methods using a moldor the like; and nanoimprint methods.

As needed, the solvent is appropriately removed (dried) from thecomposition layer applied on the support, thereby forming the film.

As the composition layer curing step, a known method may beappropriately selected depending on the curability of the bindercomponent contained in the composition, such as at least one of heatingand light irradiation, and the binder component may be cured by theselected method.

When the film of the disclosed embodiments has a pattern, as the methodfor forming the film, there may be mentioned a method comprising thestep of forming the pattern by on the composition layer by aphotolithography method or a dry etching method.

The photolithography method or the dry etching method is notparticularly limited, and it may be appropriately selected from knownmethods, depending on the binder component contained in the composition.

As another method for forming the film of the disclosed embodiments, forexample, there may be mentioned a method of shaping the film by use ofthe composition of the disclosed embodiments. The shaping method may beappropriately selected from known methods, depending on the bindercomponent contained in the composition.

The film of the disclosed embodiments is applicable to an image displaydevice and various kinds of devices including solid-state image sensingdevices such as a charge-coupled device (CCD) and a complementarymetal-oxide semiconductor (CMOS). Also, the film of the disclosedembodiments is applicable to, for example, an optical filter or lenshaving a function of absorbing or cutting a selective wavelength, acolor correction filter for color tone control, and a recording mediumusing the absorption heat of a selective wavelength.

D. Optical filter

The optical filter of the disclosed embodiments is an optical filtercomprising a color material, which is a salt-forming compound of anorganic dye with a heteropolyoxometalate,

wherein the organic dye is at least one organic dye selected from thegroup consisting of a porphyrin dye, a tetraazaporphyrin dye, aphthalocyanine dye and a squarylium dye, and

wherein the heteropolyoxometalate is a heteropolyoxometalate which hasan oxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode.

Since the optical filter of the disclosed embodiments contains theabove-specified color material which is the salt-forming compound of theorganic dye with the heteropolyoxometalate, the optical filter hasexcellent light resistance. Also, by appropriately selecting thespecific organic dye, the optical filter can selectively absorb light ina desired wavelength range, can selectively and effectively reduce thelight in the unnecessary wavelength range, and can exert a colorcorrection function for color tone control.

The optical filter of the disclosed embodiments preferably includes afilm comprising the composition of the disclosed embodiments or a curedproduct thereof, the composition comprising the above-specified colormaterial which is the salt-forming compound of the organic dye with theheteropolyoxometalate.

For the optical filter of the disclosed embodiments, a support, apressure-sensitive adhesive layer and a removable release film may belaminated on the film comprising the composition of the disclosedembodiments or the cured product thereof. The support, thepressure-sensitive adhesive layer and the removable release film may beappropriately selected from conventionally-known structures. As thepressure-sensitive adhesive layer and the removable release film,example include, but are not limited to, those described in JP-A No.2009-251511.

The optical filter of the disclosed embodiments may further comprisedifferent functional layers.

As the different functional layers, examples include, but are notlimited to, a polarizer, a protective film, an anti-reflection layer, ananti-glare layer, an anti-fouling layer, an anti-static layer, a hardcoat layer, a pressure-sensitive adhesive layer and an adhesion layer.

The optical filter of the disclosed embodiments may be such an opticalfilter, that the conventionally-known optical filter component containsthe above-specified color material which is the salt-forming compound ofthe organic dye with the heteropolyoxometalate. For example, there maybe mentioned such an optical filter that at least one of the functionallayers contains the above-specified color material which is thesalt-forming compound of the organic dye with the heteropolyoxometalate.

E. Display device

The display device of the first embodiment is a display devicecomprising the optical filter of the disclosed embodiments.

The optical filter may be incorporated into the display device and used.The method for incorporating the optical filter is not particularlylimited. The display device is not particularly limited in use orapplication.

As the display element constituting the display device, examplesinclude, but are not limited to, a liquid crystal display element, an EL(inorganic EL, organic EL) display element, a plasma display element, anelectronic paper display element, an LED display element (such as microLED) and a display element using a quantum dot light emitting diode(QLED). That is, as the display device, examples include, but are notlimited to, a liquid crystal display device, an EL (inorganic EL,organic EL) display device, a plasma display device, an electronic paperdisplay device, an LED display device (such as micro LED) and a displaydevice using a quantum dot light emitting diode (QLED).

In the case of the liquid crystal display device, a backlight is neededto be disposed on the opposite side to the molded body of the displayelement.

An example of the display device of the disclosed embodiments will bedescribed by use of a figure.

As shown in FIG. 1 , an image display device 100 mainly comprises adisplay panel 10 for displaying an image, a backlight device 20 disposedon the back side of the display panel 10, a touch panel 30 disposed onthe side closer to an observer than the touch panel 10, and a lighttransmissive adhesion layer 70 disposed between the display panel 10 andthe touch panel 30. In the disclosed embodiments, since the displaypanel 10 is a liquid crystal display panel, the image display device 100comprises the backlight device 20. Depending on the type of the displaypanel (display element), the backlight device 20 is not needed.

(Display Panel)

As shown in FIG. 1 , the display panel 10 has the structure that aprotective film 11 (such as a triacetyl cellulose (TAC) film and acycloolefin polymer film), a polarizer 12, a protective film 13, a lighttransmissive pressure-sensitive adhesive layer 14, a display element 15,a light transmissive pressure-sensitive adhesive layer 16, a protectivefilm 17, a polarizer 18, a protective film 19 are laminated in thissequence from the backlight device 20 side to the observer side. Thedisplay panel 10 includes the display element 15, and the protectivefilm 11 and so on are not always included in the display panel 10.

The display element 15 shown in FIG. 1 is a liquid crystal displayelement. However, the display element 15 is not limited to a liquidcrystal display element and may be the above-described display element,for example. The liquid crystal display element is such a displayelement that a liquid crystal layer, an alignment film, an electrodelayer, a color filter, etc., are disposed between two glass substrates.

(Backlight Device)

The backlight device 20 functions to light the display panel 10 from theback side of the display panel 10. As the backlight device 20, a knownbacklight device may be used, or the backlight device 20 may be any ofan edge light type backlight device and a direct type backlight device.As the light source of the backlight device, examples include, but arenot limited to, LED and CCFL. The backlight device which uses quantumdots as the light source, easily enhances color reproducibility.

(Touch Panel)

The touch panel 30 comprises an electroconductive film 40, anelectroconductive film 50 disposed on the side closer to the observerthan the electroconductive film 40, a light transmissive cover member 61(such as a cover glass and a resin surface material) disposed on theside closer to the observer than the electroconductive film 50, a lighttransmissive pressure-sensitive adhesive layer 62 disposed between theelectroconductive film 40 and the electroconductive film 50, and a lighttransmissive pressure-sensitive adhesive layer 63 disposed between theelectroconductive film 50 and the light transmissive cover member 61.

The electroconductive film 40 has almost the same structure as theelectroconductive film 50. That is, as shown in FIG. 1 , theelectroconductive film 40 comprises a light transmissive substrate 41, alight transmissive functional layer 42 disposed on one surface of thelight transmissive substrate 41, and electroconductive sections 44disposed on the opposite side to the light transmissive substrate 41side of the light transmissive functional layer 42 and subjected topatterning. The electroconductive sections 44 are part of anelectroconductive layer 43. The electroconductive layer 43 is composedof the electroconductive sections 44 and non-electroconductive sections45 disposed between the electroconductive sections 44. In the samemanner as electroconductive film 40, as shown in FIG. 1 , theelectroconductive film 50 comprises a light transmissive substrate 51, alight transmissive functional layer 52 disposed on one surface of thelight transmissive substrate 51, and electroconductive sections 54disposed on the opposite side to the light transmissive substrate 51side of the light transmissive functional layer 52 and subjected topatterning. The electroconductive sections 54 are part of anelectroconductive layer 53. The electroconductive layer 53 is composedof the electroconductive sections 54 and non-electroconductive sections55 disposed between the electroconductive sections 54.

The electroconductive sections are composed of a light transmissiveresin and electroconductive fibers. The non-electroconductive sectionsare composed of a light transmissive resin and do not substantiallycontain electroconductive fibers. The non-electroconductive sections mayhave a hollow in the light transmissive resin. In each electroconductivesection, the electroconductive fibers are unevenly distributed and arepresent from the half position of the thickness of eachelectroconductive section to the light transmissive substrate side ofeach electroconductive film, thereby making each electroconductivesection electroconductive from the surface thereof.

The electroconductive sections 54 of the electroconductive film 50function as the Y-direction electrode of a projected capacitive touchpanel. The electroconductive sections 44 of the electroconductive film40 function as the X-direction electrode of the projected capacitivetouch panel. Each electroconductive section includes sensors andterminals (not shown) connected to the sensors. The electroconductivesections 44 have the same structure as the electroconductive sections54; however, it is not always needed that the electroconductive sections44 have the same structure as the electroconductive sections 54.

(Light Transmissive Pressure-Sensitive Adhesive Layer)

As the light transmissive pressure-sensitive adhesive layers 62, 63,examples include, but are not limited to, a pressure-sensitive adhesivesheet such as an optical clear adhesive (OCA). Light transmissiveadhesion layers may be used in place of the light transmissivepressure-sensitive adhesive layers 62, 63.

(Light Transmissive Adhesion Layer)

The light transmissive adhesion layer 70 is present between the displaypanel 10 and the touch panel 30 and adheres to both the display panel 10and the touch panel 30. Accordingly, the display panel 10 and the touchpanel 30 are fixed. The light transmissive adhesion layer 70 is composedof a cured product of a liquid composition for curable adhesive layers,the composition containing a polymerizable compound such as an opticallyclear resin (OCR).

The thickness of the light transmissive adhesion layer 70 is preferably10 μm or more and 150 μm or less. When the thickness of the lighttransmissive adhesion layer is less than 10 μm, since the thickness istoo thin, problems such as entry of contaminants and insufficient stepfollowability are likely to occur. When the thickness of the lighttransmissive adhesion layer is more than 150 μm, the production cost istoo high. The thickness of the light transmissive adhesion layer isobtained by taking a photograph of a section of the light transmissiveadhesion layer with an optical microscope, randomly measuring thethicknesses of 10 points on the photograph, and obtaining the arithmeticmean value of the thicknesses of the measured 10 points as the thicknessof the light transmissive adhesion layer. A light transmissivepressure-sensitive adhesive layer may be used in place of the lighttransmissive adhesion layer 70.

For the image display device 100, which is the example shown in FIG. 1 ,the description in paragraphs 0018 to 0121 and FIGS. 1 to 13 of JP-A No.2018-060607 can be taken into consideration, and they are incorporatedin the DESCRIPTION.

In the image display device example shown in FIG. 1 , the optical filterof the disclosed embodiments may be disposed at a suitable position toreduce the light in the unnecessary wavelength range. For example, itmay be appropriately disposed on the side closer to the observer thanthe optical members which may be a cause for the light in theunnecessary wavelength range.

As the optical filter of the disclosed embodiments disposed in thedisplay device of the disclosed embodiments, suitable examples include,but are not limited to, a light transmissive cover member 61, a lighttransmissive pressure-sensitive adhesive layer 62, a light transmissivepressure-sensitive adhesive layer 63 and a light transmissive adhesionlayer 70.

Another example of the display device of the disclosed embodiments willbe described by use of a figure.

As shown in FIG. 2 , an image display device 101 mainly comprises adisplay panel 10′ for displaying an image, and a backlight device 20disposed on the back side of the display panel 10′. In the disclosedembodiments, since the display panel 10′ is a liquid crystal displaypanel, the image display device 101 comprises the backlight device 20.Depending on the type of the display panel (display element), thebacklight device 20 is not needed.

The backlight device 20 of FIG. 2 will not be described here, since itmay be the same as the backlight device of FIG. 1 .

(Display Panel)

As shown in FIG. 2 , the display panel 10′ has the structure that aprotective film 11, a polarizer 12, a protective film 13, a lighttransmissive pressure-sensitive adhesive layer 14, a display element 15,a light transmissive pressure-sensitive adhesive layer 16, a protectivefilm 17, a polarizer 18, a light transmissive pressure-sensitiveadhesive layer 16′, a protective film 19, a hard coat layer 80 arelaminated in this sequence from the backlight device 20 side to theobserver side. The display panel 10′ includes the display element 15,and the protective film 11 and so on are not always included in thedisplay panel 10′.

The display element 15 of FIG. 2 is a liquid crystal display element.However, the display element 15 is not limited to a liquid crystaldisplay element and may be the display element as described above.

The protective films, polarizers, light transmissive pressure-sensitiveadhesive layers and display element of FIG. 2 will not be described heresince they may be the same as those of FIG. 1 .

In general, the hard coat layer 80 of FIG. 2 is a layer which has higherhardness than protective films and which imparts at least abrasionresistance. The hard coat layer 80 preferably exhibits a hardness of Hor more in a pencil hardness test (load 4.9 N) defined in JIS K5600-5-4(1999).

The hard coat layer 80 preferably has an anti-reflection function and ananti-glare function for increasing visibility, and it may further havean anti-fouling function and an anti-static function.

The hard coat layer 80 may be selected from hard coat layers which areused in the optical filters or optical films of conventionally-knowndisplay devices. For the hard coat layer, for example, hard coat layersdescribed in International Publication Nos. WO2012/018087 andWO2011/065531, JP-A No. 2018-51918 and so on can be taken intoconsideration, and they are incorporated in the DESCRIPTION. However,the hard coat layer 80 is not limited to them.

Even in the image display device example shown in FIG. 2 , the opticalfilter of the disclosed embodiments may be appropriately disposed on theside closer to the observer than the optical members which may be acause for the light in the unnecessary wavelength range.

As the optical filter of the disclosed embodiments included in thedisplay device of the disclosed embodiments, suitable examples include,but are not limited to, the light transmissive pressure-sensitiveadhesive layer 16′ and the hard coat layer 80.

The display device of the disclosed embodiments is not limited to theabove-described examples, and conventionally-known structures may beappropriately selected and used. In the display device, the opticalfilter of the disclosed embodiments may be disposed at a suitableposition to reduce the light in the unnecessary wavelength range, forexample, and it may be appropriately selected.

EXAMPLES

Hereinafter, the disclosed embodiments will be described in detail byway of examples. The disclosed embodiments are not limited by thefollowing descriptions.

Synthesis Example 1: Synthesis of Compound 1

First, 3.82 g (1.63 mmol) of 12-molybdosilicic acid n-hydrate(manufactured by Nippon Inorganic Colour & Chemical Co., Ltd.) wasdissolved in 40 mL of methanol by heating. Next, 2.0 g (3.25 mmol) oftetraphenylporphyrin (manufactured by Tokyo Chemical Industry Co., Ltd.)was added thereto, and the mixture was stirred for one hour. Theresulting precipitate was obtained by filtration and washed with water.The obtained precipitate was dried under reduced pressure, therebyobtaining 4.67 g of the following compound 1 (yield 94%).

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 1822 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (34.65%, 2.09%,3.66%); theoretical values (34.62%, 2.11%, 3.67%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/0%/100%);theoretical values (0%/0%/100%)

Synthesis Example 2: Synthesis of Compound 2

The following compound 2 was obtained (yield 96%) in the same manner asSynthesis Example 1, except that 5.09 g (2.17 mmol) of12-molybdophosphoric acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.) was used in place of the 12-molybdosilicicacid n-hydrate (manufactured by Nippon Inorganic Colour & Chemical Co.,Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 1824 (MH₂ ⁻)

Elemental analysis values: CHN measurement values (28.87%, 1.76%,3.03%); theoretical values (28.85%, 1.76%, 3.06%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/0%/100%);theoretical values (0%/0%/100%)

Synthesis Example 3: Synthesis of Compound 3

The following compound 3 was obtained (yield 96%) in the same manner asSynthesis Example 1, except that an equimolar amount of1-vanado-11-tungstophosphoric acid n-hydrate (manufactured by NipponInorganic Colour & Chemical Co., Ltd.) was used in place of the12-molybdosilicic acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 2747 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (35.08%, 2.16%,3.73%); theoretical values (35.11%, 2.14%, 3.72%)

X-ray fluorescence analysis: V/W/Mo actual ratio (8.6%/91.4%/0%);theoretical values (8.3%/91.7%/0%)

Synthesis Example 4: Synthesis of Compound 4

The following compound 4 was obtained (yield 96%) in the same manner asSynthesis Example 1, except that an equimolar amount of1-vanado-11-molybdophosphoric acid n-hydrate (manufactured by NipponInorganic Colour & Chemical Co., Ltd.) was used in place of the12-molybdosilicic acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 1780 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (26.55%, 1.63%,2.85%); theoretical values (26.57%, 1.62%, 2.82%)

X-ray fluorescence analysis: V/W/Mo actual ratio (8.2%/0%/91.9%);theoretical values (8.3%/0%/91.7%)

Synthesis Example 5: Synthesis of Compound 5

(1) Synthesis of Intermediate 1

First, 200 g (1.22 mol) of triethylene glycol monomethyl ether(manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved indichloromethane (1.0 L). Next, 11.1 g (48.8 mmol) of benzyl triethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)and 30% NaOH aqueous solution (976 mL) was added to the resultingsolution. Then, dichloromethane solution (1.0 L) of 210 g (1.28 mol) oftosyl chloride (manufactured by Kanto Chemical Co., Inc.) was added tothe solution in a dropwise manner, and the solution was stirredovernight, thereby obtaining a reaction solution. The reaction solutionwas poured into water to divide an organic phase. The organic phase waswashed with water and then concentrated. A crude product thus obtainedwas purified by silica-gel chromatography, thereby obtaining 340 g(yield 87%) of a target intermediate 1.

The obtained intermediate 1 was confirmed to be a target compound from¹H NMR analysis results.

(2) Synthesis of Intermediate 2

First, 97.3 g (1.02 mol) of 2-formylpyrrole (manufactured by TokyoChemical Industry Co., Ltd.) was dissolved in DMF (960 mL), and theresulting solution was cooled down. To the solution, 42.1 g (1.05 mol)of 60% NaH (manufactured by Tokyo Chemical Industry Co., Ltd.) was addedat 10° C. or less in several batches, and the solution was stirred for30 minutes. To the thus-obtained solution, DMF solution (300 mL) of theintermediate 1 (340 g, 1.03 mol) was added in a dropwise manner. Thesolution was stirred overnight, thereby obtaining a reaction solution.The reaction solution was poured into ice water and extracted with ethylacetate. An organic phase thus obtained was washed with water and thenconcentrated, thereby obtaining 213 g (yield 86%) of a targetintermediate 2.

The obtained intermediate 2 was confirmed to be a target compound from¹H NMR analysis results.

(3) Synthesis of Intermediate 3

The intermediate 2 (213 g, 0.87 mol) was dissolved in DMF (860 mL).Next, 88.6 g (0.95 mol) of 4-methylpyridine manufactured by KantoChemical Co., Inc.) was added thereto, and the mixture was stirred forone hour while heating, thereby obtaining a reaction solution. Thereaction solution was cooled to room temperature, poured into ice waterand extracted with ethyl acetate. A crude product thus obtained waspurified by silica-gel chromatography, thereby obtaining 149 g (yield54%) of a target intermediate 3.

The obtained intermediate 3 was confirmed to be a target compound from¹H NMR analysis results.

(4) Synthesis of Intermediate 4

The intermediate 3 (65.6 g, 207 mmol) and 10.7 g (94.2 mmol) of squaricacid (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolvedin toluene/butanol (1/1). Next, 14.9 g (188 mmol) of pyridine(manufactured by Kanto Chemical Co., Inc.) was added thereto. Thetemperature of the resulting mixture was increased to 100° C., and themixture was stirred for hours, thereby obtaining a reaction solution.After the reaction solution was cooled down, the reaction solution wasfiltered and purified by column chromatography, thereby obtaining 1.9 g(yield 3%) of a target intermediate 4.

The obtained intermediate 4 was confirmed to be a target compound from¹H NMR analysis results.

¹H NMR (CDCl₃; δ ppm): 8.72 (d, 4H), 7.91 (d, 4H), 7.85-7.32 (m, 8H),5.09 (m, 4H), 4.00 (m, 4H), 3.44-3.11 (m, 16H), 2.50 (s, 6H)

(5) Synthesis of Compound 5

First, 2.35 g (0.70 mmol) of 1-vanado-11-tungstophosphoric acidn-hydrate (manufactured by Nippon Inorganic Colour & Chemical Co., Ltd.)was dissolved in 0.025 N hydrochloric acid (300 mL) at 60° C. Next, 1.0g (1.41 mmol) of the intermediate 4 was added thereto, and the mixturewas stirred for one hour. The resulting precipitate was obtained byfiltration and washed with water. The obtained precipitate was driedunder reduced pressure, thereby obtaining the following compound 5(yield 99%).

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 711 (MH⁺), 2747 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (23.10%, 2.40%,2.65%); theoretical values (23.02%, 2.41%, 2.68%)

X-ray fluorescence analysis: V/W/Mo actual ratio (8.5%/91.5%/0%);theoretical values (8.3%/91.7%/0%)

Synthesis Example 6: Synthesis of Compound 6

(1) Synthesis of Intermediate 5

The intermediate 3 (15.0 g, 46.9 mmol) obtained in Synthesis Example 5was dissolved in methanol, and 5%-Pd/C (manufactured by Kanto ChemicalCo., Inc.) was added thereto. The resulting solution was stirred byhydrogen bubbling at room temperature. The solution thus obtained wassubstituted with argon and then subjected to Celite filtration forconcentration, thereby obtaining 14.5 g (yield 97%) of a targetintermediate 5.

The obtained compound was confirmed to be a target compound from ¹H NMRanalysis results.

(2) Synthesis of Intermediate 6

The intermediate 5 (14.5 g, 45.5 mmol) and 2.47 g (21.7 mmol) of squaricacid (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolvedin toluene/butanol (1/1). Next, pyridine (3.49 g, 44.0 mmol) was addedthereto. The temperature of the resulting mixture was increased to 100°C., and the mixture was stirred for 5 hours, thereby obtaining areaction solution. After the reaction solution was cooled down, thereaction solution was filtered and purified by column chromatography,thereby obtaining 1.5 g (yield 10%) of a target intermediate 6.

The obtained compound was confirmed to be a target compound from ¹H NMRanalysis results.

¹H NMR (CDCl₃; δ ppm): 8.52 (m, 4H), 8.49 (m, 2H), 7.19 (d, 4H), 7.13(d, 2H), 6.30-6.08 (m, 8H), 3.75-2.91 (m, 24H)

(3) Synthesis of Compound 6

First, 2.27 g (0.70 mmol) of 1-vanado-11-tungstophosphoric acidn-hydrate (manufactured by Nippon Inorganic Colour & Chemical Co., Ltd.)was dissolved in methanol (200 mL) at 60° C. Next, 1.0 g (1.40 mmol) ofthe intermediate 6 was added thereto, and the mixture was stirred forone hour. The resulting precipitate was obtained by filtration andwashed with water. The obtained precipitate was dried under reducedpressure, thereby obtaining the following compound 6 (yield 95%).

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 715 (MH⁺), 2747 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (23.02%, 2.24%,2.70%); theoretical values (23.06%, 2.23%, 2.69%)

X-ray fluorescence analysis: V/W/Mo actual ratio (8.4%/91.6%/0%);theoretical values (8.3%/91.7%/0%)

Comparative Synthesis Example 1: Synthesis of Compound 7

The following compound 7 was obtained (yield 99%) in the same manner asSynthesis Example 1, except that 7.26 g (2.27 mmol) of12-tungstophosphoric acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.) was used in place of the 12-molybdosilicicacid n-hydrate (manufactured by Nippon Inorganic Colour & Chemical Co.,Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 2879 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (20.83%, 1.30%,2.19%); theoretical values (20.85%, 1.27%, 2.21%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/100%/0%);theoretical values (0%/100%/0%)

Comparative Synthesis Example 2: Synthesis of Compound 8

The following compound 8 was obtained (yield 99%) in the same manner asSynthesis Example 1, except that an equimolar amount of12-tungstosilicic acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.) was used in place of the 12-molybdosilicicacid n-hydrate (manufactured by Nippon Inorganic Colour & Chemical Co.,Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 615 (MH⁺), 2877 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (25.75%, 1.55%,2.71%); theoretical values (25.73%, 1.57%, 2.73%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/100%/0%);theoretical values (0%/100%/0%)

Comparative Synthesis Example 3

An intermediate 4 was synthesized in the same manner as SynthesisExample 5 and used as a compound 9.

Comparative Synthesis Example 4

An intermediate 6 was synthesized in the same manner as SynthesisExample 6 and used as a compound 10.

Comparative Synthesis Example 5: Synthesis of Compound 11

The following compound 11 was obtained (yield 96%) in the same manner asSynthesis Example 5, except that 3.14 g (0.94 mmol) of12-tungstophosphoric acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.) was used in place of the1-vanado-11-tungstophosphoric acid n-hydrate (manufactured by NipponInorganic Colour & Chemical Co., Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 711 (MH⁺), 2879 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (18.32%, 1.89%,2.16%); theoretical values (18.25%, 1,91%, 2.13%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/100%/0%);theoretical values (0%/100%/0%)

Comparative Synthesis Example 6: Synthesis of Compound 12

The following compound 12 was obtained (yield 94%) in the same manner asSynthesis Example 6, except that 3.12 g (0.93 mmol) of12-tungstophosphoric acid n-hydrate (manufactured by Nippon InorganicColour & Chemical Co., Ltd.) was used in place of the1-vanado-11-tungstophosphoric acid n-hydrate (manufactured by NipponInorganic Colour & Chemical Co., Ltd.)

The obtained compound was confirmed to be a target compound from thefollowing analysis results:

MS (MALDI) (m/z): 715 (MH⁺), 2879 (MH₃ ⁻)

Elemental analysis values: CHN measurement values (18.30%, 1.80%,2.15%); theoretical values (18.27%, 1.76%, 2.13%)

X-ray fluorescence analysis: V/W/Mo actual ratio (0%/100%/0%);theoretical values (0%/100%/0%)

Preparation Example 1: Preparation of Dispersant Solution

(1) Preparation of Block Copolymer

First, 100 parts by mass of dehydrated tetrahydrofuran (THF) and 3.00parts by mass of dimethylketene methyl trimethylsilyl acetal were put ina reactor equipped with a cooling tube, an addition funnel, a nitrogeninlet, a mechanical stirrer and a digital thermometer. Nitrogensubstitution was sufficiently carried out thereon. Next, 0.25 part bymass of a 1 M solution of tetrabutylammonium m-chlorobenzoate inacetonitrile, was injected into the reactor by a syringe. Then, a mixedsolution of 50.0 parts by mass of methyl methacrylate, 30.0 parts bymass of n-butyl methacrylate and 20.0 parts by mass of benzylmethacrylate was added in a dropwise manner for 60 minutes. The reactorwas cooled in an ice bath to keep the temperature at less than 40° C.After one hour passed, 50.0 parts by mass of glycidyl methacrylate (GMA)was added in a dropwise manner for 30 minutes. After the mixture wasreacted for one hour, 1 part by mass of methanol was added to stop thereaction. To the thus-obtained solution of the block copolymer in THF,450.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) wasadded. Solvent substitution was carried out thereon by evaporation,thereby obtaining a solution of the block copolymer in 25.0% by massPGMEA.

The thus-obtained block copolymer had a mass average molecular weight(Mw) of 11320, a number average molecular weight (Mn) of 8950, and amolecular weight distribution (Mw/Mn) of 1.26.

(2) Preparation of Phosphorus-Based Block Copolymer Solution

First, 27.80 parts by mass of PGMEA and 9.27 parts by mass ofphenylphosphonic acid (PPA) were put in a reactor equipped with acooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrerand a digital thermometer. While stirring the mixture under a nitrogenflow, the mixture was heated to a temperature of 90° C. To the mixture,100.0 parts by mass of the block copolymer was added in a dropwisemanner for 30 minutes, and the mixture was heated and stirred for twohours, thereby obtaining a phosphorus-based block copolymer (dispersant)solution (solid content 25% by mass). The progress of an esterificationreaction between the PPA and the GMA of the block copolymer wasconfirmed by acid value measurement and ¹H-NMR measurement. Thethus-obtained phosphorus-based block copolymer had an acid value of 100mgKOH/g.

Preparation Example 2: Preparation of Binder Composition

A binder composition (solid content 40% by mass) was prepared by mixingthe following: 60.0 parts by mass of PGMEA, 38.40 parts by mass of apolyfunctional monomer (“ARONIX M305” manufactured by Toagosei Co.,Ltd.) and 1.60 parts by mass of a photoinitiator (“IRGACURE 184”manufactured by BASF).

Example 1

(1) Preparation of Color Material Dispersion Liquid

First, 10.00 parts by mass of the compound 1 of Synthesis Example 1,20.0 parts by mass (solid content 25.0% by mass) of the dispersantsolution of Preparation Example 1, and 185 parts by mass of PGMEA weremixed. Using a paint shaker (manufactured by Asada Iron Works Co.,Ltd.), the mixture was subjected to a pre-dispersion for 1 hour with 2mm zirconia beads and then a main dispersion for 6 hours with 0.1 mmzirconia beads, thereby obtaining a color material dispersion liquid 1.

(2) Preparation of Color Material-Containing Binder Composition

First, 3.64 parts by mass of the color material dispersion liquidobtained in the above (1), 4.32 parts by mass of the binder compositionof Preparation Example 2, 2.05 parts by mass of PGMEA, 0.05 part by massof surfactant R08MH (product name, manufactured by DIC) and 0.05 part bymass of silane coupling agent KBM503 (product name, manufactured byShin-Etsu Silicones) were mixed. The mixture thus obtained was subjectedto pressure filtration, thereby obtaining the color material-containingbinder composition 1 of Example 1.

Examples 2 to 6

(1) Preparation of Color Material Dispersion Liquids

Color material dispersion liquids 2 to 6 were obtained in the samemanner as the above (1) of Example 1, except that the compound 1 waschanged to each of the compounds 2 to 6.

(2) Preparation of Color Material-Containing Binder Compositions

The color material-containing binder compositions 2 to 6 of Examples 2to 6 were obtained in the same manner as the above (2) of Example 1,except that the color material dispersion liquid 1 was changed to eachof the color material dispersion liquids 2 to 6.

Comparative Example 1

(1) Preparation of Comparative Color Material Solution

First, 10.00 parts by mass of tetraphenylporphyrin (manufactured byTokyo Chemical Industry Co., Ltd.) and 190 parts by mass of PGMEA weremixed. The mixture was stirred for one hour with a magnetic stir bar,thereby obtaining a comparative color material solution 1.

(2) Preparation of Comparative Color Material-Containing BinderComposition

The comparative color material-containing binder composition 1 ofComparative Example 1 was obtained in the same manner as the above (2)of Example 1, except that the color material dispersion liquid 1 waschanged to the comparative color material solution 1.

Comparative Examples 2 to 7

(1) Preparation of Comparative Color Material Dispersion Liquids

Comparative color material dispersion liquids 2 to 7 were prepared inthe same manner as the above (1) of Example 1, except that the compound1 was changed to each of the compounds 7 to 12.

(2) Preparation of Comparative Color Material-Containing BinderCompositions

The comparative color material-containing binder compositions 2 to 7 ofComparative Examples 2 to 7 were obtained in the same manner as theabove (2) of Example 1, except that the color material dispersion liquid1 was changed to each of the comparative color material dispersionliquids 2 to 7.

[Evaluation]

<Film Production and Initial Spectrometry>

Each of the color material-containing binder compositions obtained inExamples and Comparative Examples was applied onto each of glasssubstrates with a thickness of 0.7 mm (product name: OA-10G,manufactured by: Nippon Electric Glass Co., Ltd.) using a spin coater,and then heat-dried on a hot plate at 80° C. for 3 minutes, therebyobtaining coating films. The coating films were irradiated withultraviolet light at 500 mJ/cm² using an ultrahigh-pressure mercurylamp, thereby obtaining cured films having a film thickness of 3 μm. Thetransmission spectrum, chromaticity (x, y), luminance (Y) and L, a, b(L₁, a₁, b₁) of the obtained cured films were measured by MICROSCOPICSPECTROPHOTOMETER OSP-SP200 (product name, manufactured by OlympusCorporation).

At that time, the color materials deposited after the comparative colormaterial-containing binder compositions 1, 4 and 5 of ComparativeExamples 1, 4 and 5 were applied, and a uniform coating film could notbe obtained.

For the measured transmission spectrum, the transmittance difference ΔT(%) between the transmittance of the minimum transmission wavelength(the wavelength at which the transmittance is minimum) in the visiblerange (400 nm to 700 nm) and the transmittance of the baseline wasobtained. Next, the transmittance T_(1/2) (%) at which the transmittancedifference ΔT (%) was 1/2, was calculated. A half-width was calculatedfrom the difference between the maximum and minimum wavelengthssatisfying T_(1/2) (%) of a valley from the baseline, the valley givingthe minimum transmission wavelength of the transmission spectrum (i.e.,the valley width). The minimum transmission wavelength of thetransmission spectrum corresponds to the maximum absorption wavelengthof the absorption spectrum.

<Light Resistance Test>

Under the atmospheric pressure, the cured films obtained in Examples 1to 6 and Comparative Examples 2 to 3, 6 to 7 were irradiated with axenon lamp (SUNTEST XLS+(a 1.7 kW air-cooled xenon lamp) manufactured byATLAS) at a wavelength of from 300 nm to 400 nm and an irradiance of 58W/m² for 60 hours (equivalent to 11000 kJ/m²). The transmission spectrumand color coordinates (L₂, a₂, b₂) of the cured films after beingsubjected to the irradiation, were measured again.

The maximum absorption wavelength of the dyes, that is, the retentionrate of the transmittance value of the minimum transmission wavelengthof the transmission spectrum, was calculated by the following formula(1). For the porphyrin compound, the minimum transmission wavelength ofthe transmission spectrum was about 420 nm. For the squarylium compound,it was about 580 nm.The retention rate=(100−The transmittance (%) of the minimumtransmission wavelength after the test)/(100−The transmittance (%) ofthe minimum transmission wavelength before the test)×100  (1):

Also, the color difference (ΔEab) before and after the irradiation wascalculated by the following formula for light resistance evaluation.ΔEab={(L ²⁻ L ₁)²+(a ₂ −a ₁)²+(b ₂ −b ₁)²}²  (2):

The evaluation results are shown in the following Table 7.

TABLE 7 Color Oxidation- difference reduction Retention (ΔEab) potentialrate (%) before and (V) of Half- after light after light Colorheteropoly- width resistance resistance material oxometalate (nm) testtest Example 1 Compound 1 −0.232 50 94.0 10.1 Example 2 Compound 2−0.082 51 91.8 12.0 Example 3 Compound 3 0.224 52 94.5 8.2 Example 4Compound 4 0.261 52 94.8 7.5 Example 5 Compound 5 0.224 95 74.5 22.0Example 6 Compound 6 0.224 43 85.5 17.7 Comparative Tetraphenyl- — — — —Example 1 porphyrin Comparative Compound 7 −0.491 52 8.6 56.4 Example 2Comparative Compound 8 −0.495 50 59.2 40.5 Example 3 ComparativeCompound 9 — — — — Example 4 Comparative Compound — — — — Example 5 10Comparative Compound −0.491 97 4.0 79.2 Example 6 11 ComparativeCompound −0.491 44 3.2 82.1 Example 7 12

CONCLUSION

It was revealed that the films of Examples 1 to 6 using the colormaterial being the salt-forming compound of the heteropolyoxometalatehaving an oxidation-reduction potential larger than −0.3 V, haveexcellent light resistance since, compared to the films of ComparativeExamples 2, 3, 6 and 7 using the color material being the salt-formingcompound of the heteropolyoxometalate having an oxidation-reductionpotential smaller than −0.3 V, the retention rate of the transmittanceof the minimum transmission wavelength before and after the lightresistance test, is remarkably high, and the color difference before andafter the light resistance test is small. In Comparative Examples 1, 4and 5 in which the organic dyes were used as the color material, thecolor material deposited after it was applied, and a uniform coatingfilm could not be obtained. It was revealed that in the case of usingthe color material dispersion liquid and composition of the disclosedembodiments, a film with excellent light resistance can be formed whilethe desired light in the unnecessary wavelength range is selectively andeffectively absorbed and reduced. It was also revealed that the film ofthe disclosed embodiments can be used as the optical filter whichabsorbs light in the given wavelength range such as the visible range(especially 400 nm to 700 nm) and which is excellent in lightresistance.

REFERENCE SIGNS LIST

-   100, 101. Image display device-   10, 10′. Display panel-   11, 13, 17, 19. Protective film-   12, 18. Polarizer-   14, 16, 16′. Light transmissive pressure-sensitive adhesive layer-   20. Backlight device-   30. Touch panel-   40, 50. Electroconductive film-   41, 51. Light transmissive substrate-   42, 52. Light transmissive functional layer-   43, 53. Electroconductive layer-   44, 54. Electroconductive section-   45, 55. Non-electroconductive section-   61. Light transmissive cover member-   62, 63. Light transmissive pressure-sensitive adhesive layer-   70. Light transmissive adhesion layer-   80. Hard coat layer

The invention claimed is:
 1. A color material dispersion liquidcomprising: a color material, the color material being a salt-formingcompound of an organic dye with a heteropolyoxometalate; a dispersant,and a solvent, wherein the heteropolyoxometalate has anoxidation-reduction potential larger than −0.3 V relative to asilver/silver chloride electrode, and wherein the salt-forming compoundis a compound of formula (3):

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent hydrocarbongroup that the carbon atom directly bound to X¹ or X² does not have a πbond; Z⁺ represents an organic cation group; e represents an integer offrom 1 to 4; and when e is 2 or more, a plurality of Ys and a pluralityof may be each the same or different; A^(c−) represents aheteropolyoxometalate anion which is a c-valent anion and which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode; f and c are each an integer of 2 ormore; g is an integer of 1 or more; and the salt-forming compound is anormal salt that f×e=c×g.
 2. The color material dispersion liquidaccording to claim 1, wherein the heteropolyoxometalate comprisesvanadium.
 3. The color material dispersion liquid according to claim 1,wherein the heteropolyoxometalate has an oxidation-reduction potentialof 0 V or more relative to the silver/silver chloride electrode.
 4. Acomposition comprising: a color material, the color material being asalt-forming compound of an organic dye with a heteropolyoxometalate,and a binder component, wherein the heteropolyoxometalate has anoxidation-reduction potential larger than −0.3 V relative to asilver/silver chloride electrode, and wherein the salt-forming compoundis a compound of formula (3):

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent hydrocarbongroup that the carbon atom directly bound to X¹ or X² does not have a πbond; Z⁺ represents an organic cation group; e represents an integer offrom 1 to 4; and when e is 2 or more, a plurality of Ys and a pluralityof may be each the same or different; A^(c−) represents aheteropolyoxometalate anion which is a c-valent anion and which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode; f and c are each an integer of 2 ormore; g is an integer of 1 or more; and the salt-forming compound is anormal salt that f×e=c×g.
 5. The composition according to claim 4,wherein the heteropolyoxometalate comprises vanadium.
 6. The compositionaccording to claim 4, further comprising a dispersant.
 7. A filmcomprising the composition defined by claim 4 or a cured productthereof.
 8. The composition according to claim 4, wherein theheteropolyoxometalate has an oxidation-reduction potential of 0 V ormore relative to the silver/silver chloride electrode.
 9. An opticalfilter comprising a color material, wherein the color material being asalt-forming compound of an organic dye with a heteropolyoxometalate,wherein the heteropolyoxometalate has an oxidation-reduction potentiallarger than −0.3 V relative to a silver/silver chloride electrode, andwherein the salt-forming compound is a compound of formula (3):

where X¹ and X² each independently represent an aromatic ring groupoptionally containing a substituent; Y represents a divalent hydrocarbongroup that the carbon atom directly bound to X¹ or X² does not have a πbond; Z⁺ represents an organic cation group; e represents an integer offrom 1 to 4; and when e is 2 or more, a plurality of Ys and a pluralityof may be each the same or different; A^(C−) represents aheteropolyoxometalate anion which is a c-valent anion and which has anoxidation-reduction potential larger than −0.3 V relative to thesilver/silver chloride electrode; f and c are each an integer of 2 ormore; g is an integer of 1 or more; and the salt-forming compound is anormal salt that f×e=c×g.
 10. The optical filter according to claim 9,wherein the heteropolyoxometalate comprises vanadium.
 11. A displaydevice comprising the optical filter defined by claim
 9. 12. The opticalfilter according to claim 9, wherein the heteropolyoxometalate has anoxidation-reduction potential of 0 V or more relative to thesilver/silver chloride electrode.